We present two series of Cu2Ga4Te7‐based compounds with Zn substituting for Cu (Cu‐poor) and Ga (Ga‐poor), and have observed enhanced thermoelectric performance. Generally, the Seebeck coefficient (α) and lattice thermal conductivity (κL) increase and electrical conductivity (σ) decreases with the Zn content increasing. The variation in electrical properties might be mainly due to the formation of antisite defects ( and ), the acceptors. The defects increase the local density of states (DOS) near the Fermi level and effective mass, leading to the increase in α, while on the other hand, they widen the bandgap (Eg) leading to the degradation of the electrical conductivity. The gradual enhancement in κL is attributed to the reduced phonon scattering resulting from the decrease in vacancy concentration. As a result, we attained the maximum ZT value of 0.46 for Cu‐CGT and 0.47 for Ga‐CGT at ∼770 K with a proper Zn content, which is about 20–22% higher than that of intrinsic Cu2Ga4Te7.