An efficient photo‐redox strategy for the aryl‐aryl self‐coupling of aryl halides through a heterogeneous catalysis route has been demonstrated. A coordinatively unsaturated Ni2P surface with the enhanced photochemical property upon hetero‐structuring with δ‐MnO2 affects the organic transformation to biaryls with impressive yield and photo‐conversion efficiency. The dual‐role of the Ni2P catalyst with its participation as the catalytic active surface and the photo‐redox center distinguishes the organic transformation achieved herein with other catalytic and photocatalytic aryl‐aryl self‐coupling.