This study aimed to develop caffeine (CAF) orodispersible films (ODFs) and verify the effects of different percentages of film-forming agent and hydrotropic substances (citric acid—CA or sodium benzoate—SB) on various film properties. Hydroxypropyl methylcellulose E 5 (HPMC E 5) orodispersible films were prepared using the solvent casting method. Four CAF-ODF formulations were prepared and coded as CAF1 (8% HPMC E 5, CAF), CAF2 (8% HPMC E 5 and CAF:CA–1:1), CAF3 (9% HPMC E 5 and CAF:CA–1:1), and CAF4 (9% HPMC E 5 and CAF:SB–1:1). The CAF-ODFs were evaluated in terms of disintegration time, folding endurance, thickness, uniformity of mass, CAF content, thickness-normalized tensile strength, adhesiveness, dissolution, and pH. Thin, opaque, and slightly white CAF-ODFs were obtained. All the formulations developed exhibited disintegration times less than 3 min. The dissolution test revealed that CAF1, CAF2, and CAF3 exhibited concentrations of active pharmaceutical ingredients (APIs) released at 30 min that were close to 100%, whilst CAF4 showed a faster dissolution behaviour (100% of the CAF was released at 5 min). Thin polymeric films containing 10 mg of CAF/surface area (3.14 cm2) were prepared.