We report on femtosecond pump–probe experiments on two different photoinitiators in solution. These two molecules have recently appeared as attractive candidates for far-field optical lithography based on stimulated-emission-depletion (STED) inspired approaches aiming at beating Abbe’s diffraction limit. For the case of 7-diethylamino-3-thenoylcoumarin (DETC), we find that stimulated emission clearly dominates over excited-state absorption, whereas the opposite holds true for the case of isopropylthioxanthone. We argue that it is desirable that stimulated emission dominates over excited-state absorption as depletion mechanism in STED photoresists. Thus, DETC is an attractive corresponding photoinitiator.