We present the mechanisms of a remanent alignment of polarizable molecules dispersed in a solid silica gel matrix, when submitted to powerful, femtosecond, linearly polarized, optical pulses emitted from a dye laser. This alignment can be related to third‐order nonlinearities of the dopants through an orientational optical Kerr effect. Its remanence results from the strong interactions the dopants share with their host matrix, particularly through hydrogen bonds. We expose here the detailed mechanism of this phenomenon, considering that such a rotation of large chromophores may not be compatible at first sight with subpicosecond pulse durations. Through several experiments, we show that this apparent contradiction is solved once analyzed, by the structure of the excitation pulses, which cannot be simply described as ‘‘femtosecond pulses’’, but consist of two temporal components—a femtosecond one and a nanosecond one—playing different but essential roles in the process.