GeS2–CdSe superlattices and composite films are prepared by consecutive thermal evaporation of CdSe and GeS2 in vacuum. CdSe layer thickness varies between 1 and 10 nm, while the thickness of GeS2 layers is either equal (in superlattices) to or 20 times greater (in composite films) than that of CdSe layers. Standard spectral photocurrent measurements and various constant photocurrent methods are used to study optical absorption of all samples. An overall blueshift is observed with decreasing CdSe layer thickness of superlattices. This shift is related to a size-induced increase of the optical band gap of CdSe due to one-dimensional carrier confinement in the continuous nanocrystalline CdSe layers. A number of features are observed in the absorption spectra of composite films containing CdSe nanocrystals with average radii of ~2.5 and ~3.3 nm. They are discussed in terms of three-dimensional carrier confinement and are considered a manifestation of excited electron states in CdSe nanocrystals embedded in GeS2 thin film matrix. In addition to these discrete features, the exponential dependence of the optical absorption (Urbach) edge indicates a distribution of "valence band" tail states associated with disorder. Transient photoconductivity measurements made on similarly prepared SiOx–CdSe superlattices exhibit a rapid fall in photocurrent by a power law decay over several orders of magnitude of time, which is consistent with multiple-trapping transport via an extensive distribution of deep defects.