A stripy pattern of continuous epitaxial growth of thin Au nanowires on plasmonic Cu3P platelets is reported. The obtained Au–Cu3P heterostructures retain their wide area interfacial heterojunction, which is typically not observed in metal–semiconductor heterostructures. This is performed by phosphine-mediated in situ reduction of Au ions on specific facets of Cu3P platelets. The intriguing stripy movements of nanowires are regulated by strong surface binding ligands. Because this is a dual plasmon heterostructure with wide visible absorption window, these are further explored as a photoelectrocatalyst for efficient hole transfer and sensing of an important biomolecule, nicotinamide adenine dinucleotide (NADH). The observed anodic photocurrent was 30 times higher in the presence of NADH, and this proves that the heterostructured material is an ideal photosenser and an efficient catalyst for solar energy conversion.