Stacked CdTe/Zn/CdTe layers were deposited on glass substrates. The vacuum-evaporated thin films were subsequently annealed in vacuum ambience at various temperatures. Change in lattice-constant of major Cd1−xZnxTe planes against temperature was plotted from the XRD results. The graphs followed sigmoid-growth model and were regressed well by standard Boltzmann and Logistic functions. Lattice-constant varied maximum in between 375–400°C and 425–450°C, giving two separate growth trends. Optical studies suggested that presence of charge impurities and defects reduced the transmittance and band-gap values of the samples. Such reduction occurred, despite of greater formation of Cd1−xZnxTe. Decreasing granularity was however associated with increasing band-gap for samples annealed at 425 and 450°C. SEM micrographs showed that granularity decreased significantly for samples annealed at higher temperatures. EDX results were further used to co-relate the compositional characteristics with structural and optical features.