Grolleron was taught by Léon Bonnat and appeared at the Paris Salon from 1873. He painted genre scenes and several portraits, but above all history paintings and military subjects, which were greatly appreciated by the public. Among these works were A Reunion in 1870; Detatchment of French Infantry; Seated Fantassin; Defending the Road; Fight in a Factory within Paris City Walls and Soldier of the First Empire on Guard.