3D network configurations of copper(II) oxide/titanate nanobelt (CuO/TiNBs) and copper/titanate nanobelt (Cu/TiNBs) were formed using a two-step polyelectrolyte-assisted synthesis and assembly approach. The photoactivity of the TiNB/CuO and Cu/TiNB composite networks is significantly enhanced as compared to the activity of 3D structures formed of pristine TiNB. An efficient, UV-vis-light-induced electron transfer at the two-component interface achieved by the intimate coupling of TiNB with p-type semiconducting CuO and plasmonic Cu nanoparticles in composite heterostructures facilitates control over the system's exciton dynamics, which results in highly efficient UV-vis photocatalytic performance of heterostructures. The superior photocatalytic activity of the metal and semiconductor/semiconductor nanocomposite structures in the visible region is discussed, highlighting the role of interfacial electron-charge transfer (IFCT) in semiconductor-semiconductor (CuO/TiNB) and surface plasmon resonance (SPR) of Cu nanoparticles in metal-semiconductor heterostructures.