Pure and Nb-substituted CaCu3Ti4-xNbxO12+x/2 (CCTO, x = 0, 0.02, 0.1, 0.2, 0.4) ceramics were prepared by a conventional solid-state sintering, and their electric and dielectric properties were investigated using an impedance analyzer. A single-phase CCTO was obtained up to x = 0.2 Nb substitution and the lattice parameter increased with Nb substitution concentration. While the grain size decreased with Nb substitution, the resistivity of the grain boundary decreased. The dielectric constant increased with Nb substitution, and the highest value of similar to 420 000 was observed in the x = 0.2 Nb-substituted specimen at 10 kHz. The obtained electric and dielectric properties in Nb-substituted CCTO were discussed in terms of the internal barrier layer capacitor model, particularly focusing on a ratio of thickness of the grain boundary region to grain size.