The aim of this study is to develop an antioxidant film based on pea protein isolate (PPI) without sacrificing the packaging properties. To achieve this, α-tocopherol was incorporated to impart antioxidant activity to the film. We investigated the effects on film properties resulting from the addition of α-tocopherol in a nanoemulsion form and pH-shifting treatment of PPI. The results revealed that direct addition of α-tocopherol into un-treated PPI film disrupted film structure and formed a discontinuous film with rough surface, and thereby significantly decreasing the tensile strength and elongation at break. However, pH-shifting treatment in combination with the α-tocopherol nanoemulsion, formed a smooth and compact film, which greatly improved the mechanical properties. It also significantly changed the color and opacity of PPI film, but had little effects on film solubility, moisture content, and water vapor permeability. After the addition of α-tocopherol, the DPPH scavenging ability of PPI film was greatly improved and the release of α-tocopherol was mainly within the first 6 h. Additionally, pH-shifting and nanoemulsion did not affect the film’s antioxidant activity nor the release rate. In conclusion, pH-shifting combined with nanoemulsion is an effective method to incorporate hydrophobic compounds such as α-tocopherol into protein-based edible films without negative impacts on film mechanical properties.