Abstract In this study, the grafting of methyl methacrylate (MMA) in a solvent system containing nitrogen of pyridine onto LDPE films was performed using the post-irradiation technique in nitrogen at different gamma doses. The DG% obtained in MMA grafting was 71.0% at 10 kGy of γ dose was increased to 90% in (MMA/Py) (80/20 v/v%) system, indicating the existence of Py enhancement in the grafting % of MMA. The addition of pyridine (Py) into MMA matrix increases the molecular weight of the matrix due to the plasticizing effect of Py on the system. Morphological and structural changes in optical properties and thermogravimetric analysis were performed for the films. According to Fourier transform infrared data, a reaction may be placed between Py and MMA molecules. Furthermore, the effect of Py molecules on the optical properties of LDPE films is studied. The optical transition upon the grafting process increased, indicating the movement of the electrons due to intramolecular hydrogen bonds between MMA and Py molecules. The Urbach energy and the optical band gab, E g, were investigated and found to depend mainly on the grafting degree. The results obtained from E g calculations recommended using an irradiation dose of 15 kGy to get LDPE-g-MMA/Py films with suitable optical properties.