In this paper, we report the high temperature mediated structural phase transformation from B1 to B2 phase in solgel derived Cd0.2Zn0.8O nanocomposite thin film for the temperature range of 700 to 900 degree centigrade. Xray diffraction pattern provides a direct and unambiguous indication of phase evolution with increase in annealing Temperature from 700 to 900 degree centigrade along with coexistence of wurtzite phase throughout the whole transformation regime. In fact, significant reduction in lattice parameters in case of transformed B2 phase, extracted by Rietveld refinement provides a direct indication of chemical pressure inducement inside the lattice owing to anticipated mismatch in thermal expansion coefficient which leads to facilitate such phase transformation. Raman spectrum for 900 degree centigrade annealed ones, moreover, shows a distinguishable phonon mode at 866 centimeter inverse, suggesting the formation of B2 phase at higher temperature, consistent with XRD results. Scanning electron microscopy reveals the agglomeration of nanocrystallites followed by distinct void formation, indicating the evolution of chemical pressure inside the lattice. Soft Xray absorption measurement reflects a deviation of the inflection point of the absorption edge which implies Fermi level pinning with transforming phase.