Abstract: We report a facile one-pot synthesis of hollow Cu2O submicrospheres in the aqueous solution of sodium dodecyl sulfate (SDS) and polyvinylpyrrolidone (PVP). Hollow Cu2O submicrospheres with different size and porous size were prepared by changing the composition of SDS-PVP necklace-like clusters and the concentration of copper sulfate or reducing agent. The UV-vis characterization showed band gap absorption at 400-600 nm, with the decrease of the size of hollow Cu2O submicrospheres, its UV-vis characteristic absorption peaks considerably blue-shifted from the absorption of bulk Cu2O. According to the semiconductor equation, a classical Tauc approach is further employed to estimate the Eg value of hollow Cu2O submicrospheres.