The ability of a bis(germyl)ketone Ph3GeCOGePh3 to act as a photoinitiator of free radical polymerization under visible light is investigated. The results suggest that this compound could be the starting point of a new high performance class of photoinitiators. The excited state processes, as well as the generation and the reactivity of the germyl radicals, are studied by laser flash photolysis, ESR spin trapping experiments, and molecular orbital calculations; they are compared to the results obtained on a mono(germyl)ketone CH3COGePh3. Time dependent density functional theory calculations allow discussion of the strongly red-shifted ground state absorption of Ph3GeCOGePh3.