The rare-earth ions (Yb3+, Tm3+) and Li+, Bi3+ ions doped GdCa4O(BO3)3 crystals were grown using the Czochralski pulling method. The second-harmonic generation conversion efficiencies of the GdCOB:Yb and GdCOB:Tm crystals are 31.3% and 33.3%, respectively, while the undoped GdCOB crystal is 27.9%. The conversion efficiencies of Yb3+, Tm3+ doped GdCOB are improved by 12% and 19%, respectively, compared to that of the undoped one. The conversion efficiencies of Li+, Bi3+ doped GdCOB crystals are 33% and 38 3%, which are improved by 15% and 37% as compared to that of the undoped crystal. The results are discussed using the anion group theory.