Two-dimensional (2D) materials ultrathin quantum sheets have the advantage of elevating the catalysis performance and prominent edge effects, but most of them belong to element single valence materials. In this paper, the ultrathin Cu(I)/Cu(II) inorganic coordination polymer quantum sheet (ICPQS) {[Cu-II(H2O)(4)][Cu-4(I)(CN)(6)]}(n) is synthesized by controlling the appropriate molar ratio of raw material, reaction time, and temperature. Transmission electron microscopy (TEM) and atomic force microscope (AFM) analysis show that this ICPQS has a thickness of similar to 0.2 nm. Due to the fact that about 58.16% of the Cu(I)/Cu(II) is occupied in molecular structure and most of the metal active sites are fully utilized, this ICPQS can accelerate the photocatalytic degradation of methylene blue (MB) (K = 2.5 mg.L-1.min(-1) at pH 3) and organic compounds in coking wastewater and biotreated coking wastewater. Basing on mixed valences, the ICPQS can use visible light to promote energy transfer and increase quantum efficiency, paving the way for developing the next-generation monolayer 2D mixed valence photocatalysts.