Si-based cadmium sulfide (CdS) is a prospective semiconductor system in constructing optoelectronic nanodevices, and this makes the study on the factors which may affect its optical and electrical properties be of special importance. Here we report that CdS thin film was grown on Si nanoporous pillar array (Si-NPA) by a chemical bath deposition method, and the luminescent properties of CdS/Si-NPA as well as its mechanism were studied by measuring and analyzing its temperature-dependent photoluminescence (PL) spectrum. The low-temperature measurement disclosed that the PL spectrum of CdS/Si-NPA could be decomposed into four emission bands, a blue band, a green band, a red band and an infrared band. The blue band was due to the luminescence from Si-NPA substrate, and the others originate from the CdS thin film. With temperature increasing, the peak energy, PL intensity and peak profile shape for the PL bands from CdS evolves differently. Through theoretical and fitting analyses, the origins of the green, red and infrared band are attributed to the near band-edge emission, the radiative recombination from surface defects to Cd vacancies and those to S interstitials, respectively. The cause of PL degradation is due to the thermal quenching process, a phonon-induced electron escape but with different activation energies. These results might provide useful information for optimizing the preparing parameters to promote the performance of Si-based CdS optoelectronic devices. (C) 2015 Elsevier B.V. All rights reserved.