This work reports the initial study on the effect of annealing process on the crystalline phase of poly(vinylidene fluoride) (PVDF) thin film. PVDF powder was dissolved in N,N-dimethylformamide before spincoated onto a glass substrate to form a film. The films were annealed at 30°C, 90°C and 110°C for 5 hrs. The crystalline phase of the powder PVDF as received was investigated by using XRD and FTIR techniques. Moreover, the crystalline phases of thin films after annealing were investigated by using the same techniques. XRD analysis showed that in powder form PVDF exists in α-phase. Each annealed PVDF thin films exhibited identical formation of three-phases material namely γ (as major phase) while α and β phases as the minor phases. The FTIR analysis showed that the powder form of PVDF exists in α and β phases. FTIR measurement further confirmed the XRD results implying that the annealing process has no significant effect on the phase formation in PVDF films.