Poly(vinyl chloride) (PVC) undergoes photodegradation induced by ultraviolet (UV) irradiation; therefore, for outdoor applications, its photostability should be enhanced through the use of additives. Several carvedilol tin complexes were synthesized, characterized and mixed with PVC to produce thin films. These films were irradiated at 25 °C with a UV light (λ = 313 nm) for up to 300 h. The reduction in weight and changes in chemical structure and surface morphology of the PVC films were monitored. The films containing synthesized complexes showed less undesirable changes than the pure PVC film. Organotin with a high content of aromatics was particularly efficient in inhibiting photodegradation of PVC. The carvedilol tin complexes both absorbed UV light and scavenged radicals, hydrochloride, and peroxides and, therefore, photostabilized PVC.