Alfredo Muller was born in Livorno, Italy, on June 30,1869 to a wealthy Swiss family of cotton merchants. At an early age, he went to study in Florence at the schools of Giuseppe Ciaranfi and Michele Gordigiani. In 1886 he took part along with Fattori, Legi, Tommasi and the entire Post- Macchiaiolo group, in the Prima Exposizione di Bella Arti, First Exhibition of Fine Arts, in Livorno.
In 1888 his family, involoved in a bank collapse that affected half the city, decided to move to Paris. Here Muller studied first at the atelier of Francois Flameng, until 1892, and later at the atelier of Corolus-Duran. From this date on and until 1914 he stayed in the French capital, living alternately in the country, in Barbizon, in Surenses and traveling very often to Italy where he exhibited for many successive years at the Promotrici Fiorentine, Florentine Promoters. He belonged, with Toulouse-Lautrec, Jourdain, and Raffaelli to the Societe des Artistes Independants and he exhibited his work as a painter and etcher in most of the galleries of Fine Arts, Salons des Beaux Arts.
In 1903 Muller traveled to London. In 1908 he married the painter Marguerite Thomann who lived by his side for the rest of his life. In 1913 Alfredo Muller became a French citizen and the following year, at the outbreak of the First World War, he returned to Italy, first in Taormina, and later in Florence where he settled in a villa in Settignano. Muller remained in Florence almost uninterruptedly until 1930 keeping a studio and participating in numerous exhibitions, among which the most important was the Primaverile Fiorentina, Florentine Spring in 1922.
Other important exhibitions were the sucessione Romana in 1914 and the one-man exhibition at the Galleria Pesaro in Milan in 1922, and two others at the Saletta Gonnelli in Florence in 1930.
As a friend of the Gordigiani family he became very attached to Edoardo, also a painter with whom he often traveled to Striano to a villa owned by the Gordigiani family.
Muller returned to Paris in 1930 and remained there unti his death February 7, 1939.