Novel Cu2O chain-like network was assembled via a facile one-pot solution process with the assistance of poly(vinylpyrrolidone) (PVP). TEM observations showed that the chain-like structures were aggregated by hollow spheres approximately 70 nm in diameter. To be worth mentioning, HRTEM image recorded from the coherent interfacial region demonstrated that the lattice fringes penetrate from one sphere into the adjacent one smoothly without apparent diffraction contrast, which indicated that the hollow spheres experienced lattice fusion and grew into each other. Based on the systematic studies, an oriented aggregation mechanism was proposed, i.e., Cu2O nanoparticles into hollow spheres and subsequently the hollow spheres into the chain-like structures. The Raman spectra of the Cu2O chain-like hollow nanostructures were also investigated. It was found that the Raman peak intensity is different from that in the previous reports, which might be originated from the structure defect resulted from the oriented attachment.