He was born in Florence on May 29, 1835, to musician Luigi and Anna Giuliani, daughter of the famous guitarist and composer Mauro. At a very young age, he learned the rudiments of sculpture in the studio of L. Bartolini, who lived in the same building in Borgo Tinti. Around 1845, he became a student of L. Mussini, at the school the painter had founded in Florence with his friend A. Sturler, and where he studied with S. Lega.

Determined to devote himself entirely to painting, Gordigiani enrolled at the Academy of Fine Arts, attending the courses of G. Bezzuoli. During these formative years, he practiced extensively, copying the great masters of the past and began to develop excellent skills as a portraitist.

His entry to the Caffè Michelangelo dates back to 1855, where he formed friendships with the Macchiaioli group, sharing some of their research.

Soon, however, his penchant for portraiture became almost exclusive, and his refined skills in this genre quickly earned him widespread acclaim. His Self-Portrait (Uffizi Gallery), depicting himself with a subtly impudent expression and a cigar in his mouth, and his Portrait of Ludovico Raymond (Turin, Galleria Civica d'Arte Moderna) date back to 1856; his two famous portraits of the English poet Robert Browning and his wife Elizabeth Barrett (London, National Portrait Gallery) date back to 1858.

In 1860, he traveled to Paris, where he was introduced to the artistic and social circles of the city by Virginia Oldoini, Countess of Castiglione, a close friend of his, whom he portrayed several times over the years. Upon his return, he painted the portrait of Count Camillo Benso di Cavour, and in 1861, despite having only glimpsed the model at a party, he painted that of King Vittorio Emanuele II (Turin, National Museum of the Risorgimento), commissioned by his cousin Eugenio Emanuele of Savoy, Prince of Carignano.

Both canvases were presented to unanimous acclaim at the first Italian Exhibition held in Florence in 1861; on this occasion, Gordigiani refused the prize awarded to him, sharing the protests of his Macchiaioli friends against the jury, which they deemed incompetent.

The appreciation garnered by the painting of Vittorio Emanuele, however, ensured Gordigiani's rise to become the official portraitist of the House of Savoy, whose members posed several times, especially during the years when Florence was the capital.

Subsequently, other courts availed themselves of his talent, from the Portuguese (many portraits of the Savoy family are preserved in the Palacio Nacional de Ajuda in Lisbon, commissioned by Queen Maria Pia, daughter of Victor Emmanuel) to the English, where he traveled to paint the effigy of Queen Victoria. For thirty years, the painter received increasingly frequent and prestigious commissions from the nobility and wealthy bourgeoisie, even though he never failed to capture on canvas the faces of his closest family members and friends, such as the artists G. Duprè, L. Mussini, T. Conti, and the writers R. Fucini, E. De Amicis, and A. Maffei. Gordigiani's remarkable ability to faithfully reproduce human likenesses, increasingly relying on photographic models, and his adherence to the aristocratic style of the genre's finest artists active in France and England (above all, C. Duran and J.S. Sargent) are the main reasons for the success of Gordigiani's portraits, not only among his high-class clients but also among the public, who had the opportunity to admire them at major Italian and international exhibitions.

Among Gordigiani's numerous trips, most frequently to London or Paris, noteworthy is his trip to New York in 1893-94, where his son Eduardo settled and where Gordigiani was able to paint numerous portraits over the course of a few months.

After returning to Italy, he continued to produce at his usual pace almost until his death on October 7, 1909, in Florence. In April of the following year, a large portion of the paintings and sketches in his studio in Piazzale Donatello, along with numerous pieces of furniture and his art collection, were auctioned off as per his will.

In addition to portraits, Gordigiani experimented, albeit more rarely, with other types of composition, from landscapes to history paintings and genre paintings, often featuring easy subjects that were sure to appeal to the public. Modeled by his family, he occasionally dabbled in costume portraits. Constantly faithful to his own style, Gordigiani remained virtually impervious to innovation, emphasizing, as he grew older and more famous, his firm academic focus.

In addition to the aforementioned museums and numerous private collections in Italy and abroad, Gordigiani's works are held in the National Museum of Capodimonte in Naples, the National Art Gallery of Bologna, the National Gallery of Modern and Contemporary Art in Rome, and the National Gallery of Modern Art in Palazzo Pitti in Florence, where approximately thirty canvases are housed.