(100)/(001)-Oriented PZT thick films were grown on SrRuO3//(100) SrTiO3 and (100) MgO substrates by matel organic chemical vapor deposition (MOCVD) with different volume fraction of (001) orientation, and were compared with (001) single-oriented epitaxial PZT thick films grown on SrRuO3//LaNiO3//(100) CaF2 by polarized Raman spectroscopy. The spectra from (100)-oriented domain and (001)-oriented domain can be individually observed for the films with the mixture orientation of (100)/(001). Raman analysis revealed the different strain state of (100)-oriented and (001)-oriented domains. Moreover, the rotation dependence of A1(1TO) mode could be explained by the calculation using the volume fraction of (001)-oriented domains obtained from X-ray reciprocal space mapping analysis for the films with the mixture orientation of (100)/(001). These results suggest the local structure characterized by Raman spectroscopy almost agreed with the structure characterized by XRD analysis for the films with the mixture orientation of (100)/(001).