Raman scattering spectra and ferroelectric properties of epitaxial tetragonal Pb(Zr, Ti)O3 were investigated for polar axis-oriented thin films with various Zr/(Zr + Ti) ratios and by changing the ratios from 0 to 0.50 at different measurement temperatures. The chosen films in the thickness range of 1–2 μm present the advantage of showing small residual strain. The E (TO) modes were successfully isolated using cross-polarization configurations, while A1 (TO) and B1 modes were activated using parallel polarization configurations. Systematic changes in Raman peak positions were observed with changes in the Zr/(Zr + Ti) ratios at different measurement temperatures. It was found in both cases that the tetragonal distortion (c/a-1) and the value of square of spontaneous polarization (Ps2) linearly increased with increasing ω2[A1(1TO)], where a and c are the lattice parameters of a and c-axes. This indicates that monitoring A1(1TO) mode is efficient as a characterization method of ferroelectricity. It can also be used as a novel nondestructive process check or reliability assessment technique during fabrication of microelectromechanical systems (MEMS) using piezoelectric materials.