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In this work, the optimal conditions for the electrodeposition of a CdSe film on n-Si were demonstrated. The structural and optical properties of the bare films and after annealing were studied. In particular, the crystallinity and photoluminescence of the samples were evaluated, and after annealing at 400 °C under a nitrogen atmosphere, a PL increase by almost an order of magnitude was observed. This paper opens the route towards the use of electrochemical deposition as a cost-effective and easy fabrication approach that can be used to integrate other interesting materials in the silicon-manufacturing processes for the realization of optoelectronic devices.