Samain was born in Nivelles, and studied at the Académie Royale des Beaux-Arts in Brussels under Louis Simonis. After winning the Belgian Prix de Rome, he lived for a time in Italy. In 1889, he was awarded a gold medal at the Paris Exposition Universelle, and in 1895 his work was shown at the Société des Artistes Français in Paris. He died in Ixelles.