The article reports on the influence of annealing PVDF in an autoclave process on the PVDF phase composition. DSC, FTIR and XRD measurements serve to observe the phase changes in an already stretched, polarised and β-phase rich film. Annealing was conducted between 90 and 185 ∘C to cover a broad range of curing processes in an autoclave. The β-phase is found to be stable up to near the melting range at 170 ∘C. At 175 ∘C, the non-piezoelectric α-phase dominates and the piezoelectric γ- and γ′-phases appear. The γ-phase grows at elevated temperatures and replaces the β-phase. This observation stresses the importance of developing new methods to reactivate the polarisation after annealing, in particular for the integration of PVDF as a sensor in laminated structures, such as CFRP.