Léon Fontaine began his career in the coal industry, in Flénu, his native region, where his uncle was a mining company administrator. He was listed there as an assistant engineer. From 1873 onwards, he was appointed Vice-Consul of Spain in Brussels — a role that reflects his integration into the influential circles of the commercial and industrial bourgeoisie.
Léon Fontaine married Marie Pauline Eugénie van der Straeten in 1875. Together, they had four daughters: Odile, Gabrielle, Marguerite, and Suzanne.