In this communication, the novel nonlinear optical crystal material Cd4BiO(BO3)(3) with 3-chromophore asymmetric structures of CdOn, BiO6, and BO3 groups has been prepared by a flux method, and the single crystal structure has been determined with the space group Cm. It is the largest NLO coefficient for Cd4BiO(BO3)(3) among borate systems, and the strong NLO response originates from cooperation effects of the 3-chromophore asymmetric structures composed of the polar displacement of d(10) Cd2+ ion, stereochemically active lone pair of Bi3+, and pi-delocalization of BO3. These evidence are provided in view of evaluations of calculated density of states and electron-density difference maps. The experimental measurements show that the features of a large SHG effect. phase-match. and high thermal stability will be favorable in industrial production and applications for Cd4BiO(BO3)(3).