Photocatalytic and electrocatalytic reactions to produce value-added chemicals offer promising solutions for addressing the energy crisis and environmental pollution. Photocatalysis is driven by light excitation and charge separation and relies on semiconducting catalysts, while electrocatalysis is driven by external electric current and is mostly based on metallic catalysts with high electrical conductivity. Due to the distinct reaction mechanism, the conversion between the two catalytic types has remained largely unexplored. Herein, by means of density functional theory (DFT) simulations, we demonstrated that the ferroelectric heterostructures Mo-BN@In2Se3 and WSe2@In2Se3 can exhibit semiconducting or metallic features depending on the polarization direction as a result of the built-in field and electron transfer. Using the nitrogen reduction reaction (NRR) and hydrogen evolution reaction (HER) as examples, the metallic heterostructures act as excellent electrocatalysts for these reactions, while the semiconducting heterostructures serve as the corresponding photocatalysts with improved optical absorption, enhanced charge separation, and low Gibbs free energy change. The findings not only bridge physical phenomena of the electronic phase transition with chemical reactions but also offer a new and feasible approach to significantly improve the catalytic efficiency.