In this paper, we synthesized layered crystals of bis(μ₂-chlor)-tris(triphenylphosphine)-di-copper(I) (CTC) and bis(μ₂-bromo)-tris(triphenylphosphine)-di-copper(I) (BTC) via electrochemical synthesis in an ambient environment. The crystal stands edge-on to the copper substrate in the electrochemical synthesis, which would enhance the charge transfer between the crystal and the substrate, promoting its photoelectric properties. Combined with density functional theory calculations, the optical absorption and emission are the crystals were studied to obtain a clarified mechanism. Using a chemical etching strategy, we can obtain BTC microtubes with tunable cavities, which can be used as microscopic containers.