In prospective of fabrication of lucrative solar cells, cadmium selenide (CdSe) is an outstanding absorber layer contender whose electrical response and structural features could be amended by Bismuth dopant. Annealing is momentous approach in modulation of properties of CdSe:Bi films where optimization of annealing temperature is indispensable. Current research work focuses on modulation of physical characteristics of thermally grown CdSe:Bi 3% layers which are annealed in 150–350 °C range. Crystallographic investigation unveils growth of polycrystalline CdSe:Bi layers where crystallite size with respect to (111) strongest reflection is ranged between 32 nm and 41 nm. Optical exploration divulges that maximum visible light-absorption is exhibited by 150 °C annealed films. Photoluminescence spectra demonstrate higher intensity of PL peak centered at ∼685 nm for pristine films. Electrical features disclose development of Ohmic contacts where conductivity is strengthened at 150 °C. AFM analysis specifies mound-like topography for pristine samples whereas annealed CdSe:Bi films designate hill and spike-like topographies with variable density.