Si nanoclusters (Si-nc) embedded in SiO2 present outstanding luminescent emission in the visible and are the material of choice for the realization of efficient light sources integrated with Si technology. PECVD is an attractive preparation route but there is still the need to understand how Si excess and matrix composition affect the precipitation of Si-nc and their photoluminescence (PL) efficiency. The SiOx PECVD layers studied here have a Si excess up to 50% and a thickness between 50 and 100 nm. The phase separation, precipitation and growth of the Si-nc have been achieved by annealing at 1250 °C. For reference, the same study has been performed in Si-nc/SiO2 materials synthesized by ion implantation and annealing. Refractive index and thickness measured by ellipsometry show a densification of the layers after the H release during annealing. A detailed composition profile has been determined by XPS and FTIR analyses and shows almost complete phase separation except for the interfaces, where a depletion of Si-nc is found. EFTEM demonstrates that isolated Si-nc are formed for Si excess up to 25% while for higher Si excess a continuous Si phase is observed. The PL efficiency in PECVD samples is maximized for a Si excess of 17% which is the same Si excess than that for the most emitting implanted samples. No dependence of PL efficiency has been found on the presence of Nitrogen in the matrix (up to the 10%).