The van der Waals epitaxy of functional materials provides an interesting and efficient way to manipulate the electrical properties of various hybrid two dimensional (2D) systems. We study the controlled epitaxial assembly of semiconducting one-dimensional (1D) atomic chains, AuCN, on graphene and investigate the electrical properties of 1D/2D van der Waals heterostructures. AuCN nanowire assembly is tuned by different growth conditions, although the epitaxial alignment between AuCN chains and graphene remains unchanged. Semiconducting AuCN chains endow the 1D/2D hybrid system with a strong responsivity to photons with an energy above 2.7 eV, which is consistent with the bandgap of AuCN. A large UV response (responsivity ∼104 A/W) was observed under illumination using 3.1 eV (400 nm) photons. Such optical and electrical responses are changed by tuning the morphology of AuCN nanowires. Our study clearly demonstrates that 1D chain-structured semiconductors can play a crucial role as a component in multifunctional van der Waals heterostructures.