Two hybrid polyacrylamide chiral stationary phases (CSPs) for HPLC have been synthesized by a new surface-initiated photo-induced radical polymerization approach of enantiopure N,N'-diacryloyl derivatives of (1R,2R)-diaminocyclohexane (CSP1) and (1R,2R)-diphenylethylenediamine (CSP2). This system is based on the activation of mesoporous silica microparticles by chemically bonded trichloroacetyl groups and dimanganese decacarbonyl as catalyst. UV irradiation was performed using a lab-made quartz photochemical reactor, ad hoc designed for the photo-induced polymerization process on the surface of microparticles. The two phases were evaluated and compared as chromatographic supports for the enantioselective HPLC of model chiral compounds. Their physico-chemical properties and chromatographic performances were also evaluated in comparison with those exhibited by the homologue CSPs obtained by the grafting-from thermal-induced process (CSP3 and CSP4). The new photopolymerization approach yielded higher grafting density than the thermal-induced one, especially in the case of the less reactive monomer (the diacryloyl derivative of (1R,2R)-diphenylethylenediamine), good chromatographic efficiency and a broad application field under normal phase and polar organic mode conditions.