The controllable synthesis of noble metal alloy nanostructures with highly branched morphology has attracted much attention because of their specific physical and chemical properties. This article reports the synthesis of platinum-copper bimetallic alloy nanodendrites (Pt-Cu BANDs) by a facile, one-pot, templateless, and seedless hydrothermal method in the presence of poly(allylamine hydrochloride) (PAH) and formaldehyde (HCHO). The morphology, composition, and structure of Pt-Cu BANDs are fully characterized by various physical techniques, demonstrating Pt-Cu BANDs are highly alloying, porous, and self-supported nanostructures. The formation/growth mechanism of Pt-Cu BANDs is explored and discussed based on the experimental observations. The autocatalytic growth and interdiffusion are responsible for the formation of Pt-Cu alloy whereas selective oxidative etching results in dendritic morphology of Pt-Cu alloy nanostructures. In addition, the electrocatalytic activity and stability of Pt-Cu BANDs for the methanol oxidation reaction (MOR) are investigated by various electrochemical techniques. The synthesized Pt-Cu BANDs show higher electrocatalytic activity and stability than commercially available Pt black.