Two new mixed metal fluoride carbonates, KCdCO3F and K2Pb3(CO3)(3)F-2, have been synthesized by solvothermal and solid-state techniques. KCdCO3F crystallizes in the acentric nonpolar space group P (6) over bar m2, and its structure features a three-dimensional anionic framework in which the CdCO3 layers are further interconnected by bridging F anions with the negative charge balanced by K+ cations. K2Pb3(CO3)(3)F-2 crystallizes in the centrosymmetric space group P6(3)/mmc, and its structure exhibits a layered anionic skeleton featuring corner-shared PbO6F and PbO6F2 polyhedra. UVvis diffuse reflectance spectroscopy studies show that the short-wavelength absorption edges of KCdCO3F and K2Pb3(CO3)(3)F-2 are 227 and 287 nm, respectively. The second harmonic generation (SHG) measurement reveals that KCdCO3F is a phase-matchable material for generation of doubled-frequency light at both 532 and 266 nm, with a large SHG response of approximately 5.2 times that of KH2PO4 (KDP) at 532 nm and a moderate SHG response of approximately 0.75 times that of beta-BaB2O4 (BBO) at 266 nm. Therefore, it is a promising UV material for fourth harmonic generation on a 1064 nm Q-switched Nd:YAG laser.