Owing to the very brittle nature of tellurium powder, nanoscopic grains with an average size of 4.8 ± 0.8 nm were produced by dry vibration milling technique using a mixer/mill apparatus. A novel material was obtained by binding the nanosized tellurium grains with poly(methyl methacrylate) (PMMA) polymer. The morphology, elemental composition, and structural and optical properties of Te/PMMA films were investigated. The prepared material was composed of hexagonal tellurium and α-phase of tellurium oxide. The electrical properties of the films were studied, for different electrode contact configurations, in dark condition and under white light illumination varying the optical power density from 2 to 170 mW/cm(2) and turning the light on and off cyclically. Data analysis shows that the photoconductivity of the film with sandwich contact configuration is a linear function of the light power density and increases more than 2 orders of magnitude as compared to the photoresponse of the film with coplanar contact configuration.