First-principles density functional theory (DFT) calculations have been used to investigate the structural and electronic properties of the cubic KCaF3 and NaCaF3 (001) surfaces with MF (M = K or Na) and CaF2 terminations. For both KCaF3 and NaCaF3 (001) surfaces, the MF termination has stronger surface rumpling than the CaF2 termination. All the computed band gaps for the KCaF3 and NaCaF3 (001) surfaces are smaller than those of the bulks. Furthermore, separated bands that originate from surface layer Fp states are introduced at the top of the valance band of MF-terminated surfaces, indicating the emergence of the surface states. The calculated surface energies show that the MF-terminated surface is energetically more favorable than the CaF2-terminated surface.