This report outlines the construction of an advanced, exquisite photoswitchable enzyme cascade on the basis that tyrosinase (TYR) catalyzes the generation of dihydroxyphenylalanine (DOPA) coordinated TiO₂ nanoparticles (NPs) to form a light responsive nano-trigger that subsequently photoactivates the enzymatic activity of horseradish peroxidase (HRP). This photoswitchable enzyme cascade has a powerful signal transduction/amplification ability in TYR-based bioassays, and holds great promise to be applied in versatile applications.