•CBD-CdSe thin films were successfully prepared for temperatures in the range 0–80 °C.•Phase transformation of CBD CdSe NPs was obtained by varying the growth temperature.•Depending on Temperature the particle size can take values in the 7–12 nm range.•CdSe NPs bandgap as function of T show evidence of the effect of the phase transition.•The Raman spectrum for Tbc shows modes related with the disorder of the CdSe lattice. Structural and electronic properties characterization results show that the crystallographic structure of CdSe films, deposited by chemical bath synthesis, is controlled by the bath growth temperature. The synthesis parameters employed produced a set of nanostructured CdSe films on glass substrates with controlled crystal structure. The effect of bath temperature (Tb) on CdSe films was studied in the 0 ≤ Tb ≤ 80 °C range. The average crystal diameter (AD) of the films lies within the 7 ≤ AD ≤ 12 nm interval, where AD depends on the selected Tb. X-ray diffractograms (XRD) shown that at low Tb values the formation of the hexagonal wurtzite (WZ) is promoted while at the other extreme the cubic zinc-blende (ZB) crystalline structure dominates. It is observed that the WZ → ZB transition occurs at the critical temperature Tbc ~ 40 °C. The AD in each films for CdSe-NP’s was obtained from XRD analysis employing the Scherrer-Debye formula. The values of the lattice interplanar spacing (IS), determined from XRD analysis, as function of Tb increases continuously except at temperatures around Tbc where a local minimum is observed. The presence of stress acting on CdSe NP’s is identified by correlating the IS values with the crystalline structure: compression occurs for 0 ≤ Tb ≤ 40 °C, and tension for 50 ≤ Tb ≤ 80 °C. The band gap energy, obtained from optical absorption spectra, decreases monotonically but a local minimum is observed at Tbc = 40 °C. Results from Raman spectroscopy show that the CdSe Raman LO-mode hardens for Tbc as consequence of the WZ ↔ ZB structural transition.