The Stark spectrum of Ca atom with m = 0 in the vicinity of n = 10 to n = 13 have been obtained by using two-step excitation and photoionization methods in the applied electric field from 0 to 8 kV/cm. The experimental results show that the 3d2 3P0 and 3d2 3P2 valence states are repelled by n= 12 Stark manifold. The interaction among the zero-field non-degenerate states, valence states and Stark states are discussed. The interference phenomenon, in which valence state and Stark states take part, has been observed. The interference is enhanced when the electric field increase.