A diffractive sail is a solar sail whose exposed surface is covered by an advanced diffractive metamaterial film with engineered optical properties. This study examines the optimal performance of a diffractive solar sail with a Sun-facing attitude in a typical orbit-to-orbit heliocentric transfer. A Sun-facing attitude, which can be passively maintained through the suitable design of the sail shape, is obtained when the sail nominal plane is perpendicular to the Sun–spacecraft line. Unlike an ideal reflective sail, a Sun-facing diffractive sail generates a large transverse thrust component that can be effectively exploited to change the orbital angular momentum. Using a recent thrust model, this study determines the optimal control law of a Sun-facing ideal diffractive sail and simulates the minimum transfer times for a set of interplanetary mission scenarios. It also quantifies the performance difference between Sun-facing diffractive sail and reflective sail. A case study presents the results of a potential mission to the asteroid 16 Psyche.