Photoluminescence (PL) of nanocrystalline Si (nc-Si) assemblies formed by thermal crystallization of amorphous Si/SiO2 and SiO/SiO2 superlattices (SLs) has been investigated at different temperatures and excitation conditions. The low temperature resonant PL spectroscopy reveals phonon-assisted excitonic recombination. At room temperature the samples formed from a-SiO/SiO2 SLs possess relatively high PL quantum yield (∼ 1%). The PL transients have non-exponential decay, which indicates the exciton energy transfer in nc-Si ensembles. The excitonic energy of Er-doped nc-Si SL structures can be almost completely transferred to Er ions incorporated in SiO2 matrix that results in a strong emission line at 0.81 eV.