Amorphous lead–zirconate–titanate (Pb 0.97Nd 0.02(Zr 0.55Ti 0.45)O 3, PNZT) thin-films were grown on single-crystal MgO(1 0 0) substrates at room temperature by pulsed laser deposition (PLD). Part of PNZT films was left as-deposited amorphous and others were post-annealed at temperatures from 100 to 400 °C. X-ray diffraction (XRD) and scanning probe microscopy (SPM) were used to characterize the microstructure. Optical properties were analyzed using spectrophotometry at UV–vis–NIR and prism-coupler method at 633 nm wavelengths. Initially, films were amorphous with a broad XRD peak around 2 θ ≈ 29.7°. As the post-annealing temperature increased above 250 °C, the amorphous peak started to shift towards lower 2 θ-angles and got narrower indicating of decreasing interatomic spacing and possible glass transformation. At the same time, the transmittance at all wavelengths increased remarkably, although no crystal structure was detected by XRD. Also, sharp optical TE 0 modes with full-width half-maximum (FWHM) values of Δ β ≈ 0.00067 could be coupled into these films.