This paper presents a comparative study of the photoinduced electron transfer in a series of donor-acceptor compounds and their hydrogen-bonded complexes in solution. 4-(Dimethylamino) pyridine III, similarly to 4-(dimethylamino) pyrimidine I and 4-(dimethylamino)-5-methylpyrimidine II and contrary to 4-(N,N-dimethylanilino) pyrimidine IV, shows dual luminescence in a sufficiently polar and mobile environment. The results of steady-state and kinetic investigations as well as quantum chemical calculations of I-III fit well into the twisted intramolecular charge transfer (TICT) state model. On the other hand, the results suggest an enhanced planarity of the ICT fluorescent state of IV. INDO/S calculations confirm the large probability of the allowed radiative transitions in the latter compound. Photophysics of all the compounds under study is modified by hydrogen bonding: fluorescence quantum yields are strongly reduced in the presence of alcohols.