Room temperature photoluminescence (PL) at 1.54 mm from erbium-doped silicon rich silicon oxide (ErSRSO) films, fabricated on fused quartz by thermal evaporation followed by thermal-annealing in air, is reported. PL measurements show maximum intensity in samples annealed at 1000 C for 4 h. X-ray diffraction (XRD) structural analyses show that annealing caused the formation of active Er 3þ (Er 2 O 3 ) centers. XRD and PL results show that increasing Er 2 O 3 concentration does not necessarily lead to an increase in photoluminescence. Compositional analysis using time-of-flight secondary ion mass spectroscopy (TOF-SIMS) depth-profiling shows a strong correlation between the presence of contiguous Si rich regions and Er 2 O 3 centers on the one hand and the observed PL on the other. The combination of PL, XRD, and TOF-SIMS results indicate the presence of silicon clusters and its sensitization of erbium. These results are consistent with the literature reported decomposition of SiO x at elevated temperatures which in turn leads to the formation of Si clusters in the silicon oxide matrix.