Graphene oxide (GO) is a photoluminescent material whose application in optoelectronics has been strongly limited due to its poor emission intensity. In this work, a GO–porous silicon (GO–PSi) hybrid structure is realized in order to investigate the emission properties of GO infiltrated into a porous matrix. GO–PSi is characterized by Fourier transform infrared spectroscopy, spectroscopic reflectometry, and steady-state photoluminescence. A photoluminescence enhancement by a factor of 2.5 with respect to GO deposited on a flat silicon surface is demonstrated. Photoluminescence measurements also show a modulation of the emitted signal; this effect is attributed to the interference phenomena occurring inside the PSi monolayer.