It has been demonstrated that copper can be selectively deposited on a variety of substrates including Teflon (polytetrafluoroethylene or PTFE), Kapton (polyimide resin), silicon and gallium arsenide from solution by photo-assisted initiated deposition. A copper containing solution was prepared from a mixture of copper(I) chloride (Cu2Cl2) and decaborane (B10H14) in diethyl ether and/or THF (tetrahydrofuran). The copper films were fabricated by ultraviolet photolytic decomposition of copper chloride and polyhedral borane clusters. This liquid phase deposition has a gas-phase cluster analog that also results in copper deposition via pyrolysis. The approach of depositing metal thin films selectively by pholysis from solution is a novel and an underutilized approach to selective area deposition.