The meta-PPV copolymer was prepared by the condensation of the diphosphonium chloride of meta-xylene with dialdehyde of vanillin. Meta-PPV thin films were successfully deposited on glass substrates by spin casting method. The polycrystalline structure of the films was confirmed using X-ray diffraction (XRD) analysis, and also XRD was utilized to compute the grain size and dislocation. Surface morphology was characterized by using photomicroscope and scanning electron microscopy. Fourier-transform infrared spectroscopy was used to verify the presence of the absorbance bands. The optical absorption measurement revealed direct-allowed electronic transition with band gaps 3.3 eV and 2.85 eV for as-deposited and annealed films, respectively. The redshift of the band gap and related optical constant after annealing was assigned to the change in configuration and conformation of copolymer chains. Thermal annealing leads to the reduction in PL efficiencies and redshift of single peak which attributed to band-to-band transition.