ZnO thin films were synthesised by a new method which uses polyvinyl alcohol (PVA) as the polymer precursor. The films are annealed at different temperatures and for different annealing times. The structural parameters, like grain size, lattice constants, optical band gap, and Urbach energy, depend on the annealing temperature and time. All the films possess tensile strain, which relaxes as the annealing temperature and time increase. The photoluminescence (PL) spectra contain only ultraviolet (UV) peaks at low temperature, but as the annealing temperature and time increase, we observe peaks at the blue and green regions with a variation in the intensities of these peaks with annealing temperature and time. The thin films were synthesized by a new method which uses polyvinyl alcohol (PVA) as the polymer precursor. The films are annealed at different temperatures and for different annealing times. The structural parameters, like grain size, lattice constants, optical band gap, and Urbach energy, depend on the annealing temperature and time. All the films have tensile strain, which relaxes as the annealing temperature and time increase. The photoluminescence (PL) spectra contain only ultraviolet (UV) peaks at low temperature, but as the annealing temperature and time increase, we observe peaks at the blue and green regions with a variation in the intensities of these peaks with annealing temperature and time.