The results of the spectral and photophysical investigations of 4-dimethylaminopyridine (DMAP), 4-diethylaminopyridine (DEAP), 4-diisopropylaminopyridine (DIAP) and their 1: 1 complexes with alcohols under supersonic jet conditions by LIF, R2PI and IR/R2PI techniques are presented. The dispersed emission spectra of jet-cooled DMAP, DEAP and DIAP, recorded upon selective excitation in the 0(0)(0) region, are attributed mostly to the radiative transition from the primary excited state. In the case of DIAP the higher energy excitation results in an appearance of the long-wave fluorescence. The low-energy luminescence band is observed also for the complexes of DEAP and DIAP with alcohols of relatively strong acidity. (C) 2008 Elsevier B. V. All rights reserved.