Pure poly(dimethylsiloxane) (PDMS) films, PDMS-nanodiamond (ND) and pure nanodiamond powder were irradiated with 2 MeV protons under a variety of fluence and current conditions. Upon proton irradiation, these samples acquire a fluence-dependent photoluminescence (PL). The emission and excitation spectra, photostability and emission lifetime of the induced photoluminescence of PDMS and PDMS-ND samples are reported. Pure PDMS exhibits a noticeable stable blue PL, while the PDMS-ND composites exhibit a pronounced stable green PL under 425 nm excitation. The PL of PDMS-ND composites is much more prominent than that of pure PDMS or pure ND powder even when irradiated at higher doses. The origin of the significantly enhanced PL intensity for the proton-irradiated PDMS-ND composite is explained by the combination of enhanced intrinsic PL within ND particles due to ion-implantation-generated defects and by PL originating from structural transformations produced by protons at the nanodiamond/matrix interface.