Mucoadhesive buccal film is developed as a promising dosage form, which has prominent advantages because of drug delivery through buccal mucosa. New formulation of buccal films containing rizatriptan benzoate (RB) was prepared by solvent casting method using various concentrations of hydroxypropyl methylcellulose (HPMC K4M), polyvinyl alcohol (PVA), polyethylene oxide (PEO), glycerol, stevia, and goat buccal mucosa used as a model membrane. In this work, the effect of polymers and plasticizer concentrations on drug release profile, disintegration and dissolution time, mechanical properties, and mucoadhesive characteristics of films was studied. Scanning electron microscopy analysis revealed uniform distribution of RB in film formulations. Chemical compounds and thermal analysis of the films were studied by Fourier transform infrared spectroscopy and differential scanning calorimetry, respectively. The buccal films produced were uniform in drug content and thickness. All formulations have in vitro release of 98–102% between 40 and 80 min. Also ex vivo mucoadhesion strength was in the range of 0.205 ± 0.035 to 0.790 ± 0.014 N for all formulations. A formulation consisting RB (50 mg), HPMC K4M, PVA, and PEO (63 mg), glycerol (1.5 ml), stevia (5 mg) was selected as our optimum composition. More satisfactory results were obtained in terms of disintegration and dissolution time, mechanical properties, and mucoadhesive characteristics. In addition, it showed about 99.89% RB released in 45 min. The results suggest that RB-loaded mucoadhesive buccal films could be a potential candidate to achieve optimum drug release for effective treatment of migraine.