Vincenzo Irolli was born in Naples on September 30, 1860. He received his artistic training at the city's Institute of Fine Arts.

In 1879, he participated for the first time in the 15th Exhibition of the Società Promotrice in Naples, exhibiting Felice Rimembranza (Happy Remembrance), a work that won him a prize. The following year, he returned with historical paintings, while in subsequent years he focused on genre scenes, studies from life, and portraits. Domenico Morelli took favorable note of Irolli’s portraiture skills, particularly his use of color and bold brushwork.

He took part in various national exhibitions: the 1884 General Italian Exhibition in Turin and the 1887 National Exhibition in Venice; meanwhile, at the 1891 Società Promotrice exhibition in Naples, his painting Primavera (Spring) was purchased by Victor Emmanuel III.

In 1893, he sent La prediletta (The Favorite) and Cavalleria rusticana to Rome—the latter receiving an honorable mention—and exhibited them again in Milan in 1894 alongside Le prime mammole (The First Violets). Also in 1894, his painting Il Natale a Napoli (Christmas in Naples)—featured in the magazine Moderne Kunst—was sold in Berlin for the substantial sum of 23,000 lire. In 1897, he exhibited Sogno primaverile (Spring Dream) in Milan; it was purchased for the Mulhouse Museum in France.

During this period, Irolli devoted himself primarily to genre scenes—depicting mothers with their children in domestic settings, common folk, and young brides—all rendered with his distinctive fluid and textured brushwork.

Irolli continued to participate in major national and international exhibitions throughout the twentieth century. The Italian Exhibition in London in 1904, the Paris Salon and the International Exhibition in Angers the following year, and the National Exhibition in Milan in 1906.

He also participated in the International Exhibition in Barcelona—featuring genre scenes—and, from 1913 onwards, in major Italian exhibitions in Naples, Florence, and Venice.

During the 1930s, he held solo exhibitions in various Italian cities.

The last exhibition in which he took part was the 1st National Annual Exhibition in 1948 in Cava de' Tirreni.

He passed away in Naples on November 27, 1949.

His works are housed in major national galleries and numerous private collections.