Lead-zirconate-titanate Pb0.97Nd0.02(Zr0.55Ti0.45)O3 films were grown on MgO(100) substrates at room temperature by pulsed laser deposition. Films were left amorphous or post-annealed at temperatures from 100°C to 400°C. X-ray diffraction, Raman spectroscopy, scanning electron microscopy, spectrophotometry, and prism-coupler methods were used for characterization. Initially amorphous films went through glass transformation when post-annealing temperature increased above 250°C and above 300°C, Raman spectroscopy revealed Pb–O and Ti–O7 vibration modes. At the same time, surfaces flattened to Rq ≈ 2–5 Å, transmittance increased remarkably, and very sharp optical modes Δβ ≤ 0.00046 could be coupled into films.