The manufacturing of semiconducting films using solution-based approaches is considered a low cost alternative to vacuum-based thin film deposition strategies. An additional advantage of solution processing methods is the possibility to control the layer nano/microstructure. Here, we detail the production of mesoporous CuGaS2 (CGS) and ZnS layers from spin-coating and subsequent cross-linking through chalcogen-chalcogen bonds of properly functionalized nanocrystals (NCs). We further produce NC-based porous CGS/ZnS bilayers and NC-based CGS–ZnS composite layers using the same strategy. Photoelectrochemical measurements are used to demonstrate the efficacy of porous layers, and particularly the CGS/ZnS bilayers, for improved current densities and photoresponses relative to denser films deposited from as-produced NCs.