A pronounced photoluminescence enhancement on chemically oxidized porous silicon was induced by a series of organic cyano compounds including 1,2-dicyanoethylene (CE), 1,3-dicyanobenzene (1,3-CB), 1,4-dicyanobenzene (1,4-CB), 1-cyanonaphthalene (1-CN), and 9-cyanoanthracene (9-CA). Photoluminescence enhancement effects were reversible for all compounds studies in this work. A dependence of photoluminescence enhancement on the steric effect and the electronic characteristics of these compounds and the structure of the porous silicon substrates were analyzed in terms of the photoluminescence enhancing factors. Surface chemical composition examined by Fourier transform infrared (FTIR) spectra demonstrated that the surface Si-H bonds were not changed and no new luminescent compounds were formed on porous silicon surface during adsorption of cyano compounds. A mechanism based on induced surface states acting as radiative recombination centers by cyano compounds adsorption was suggested.