• A high ZT of ~0.52 is achieved in n -type (Ag, Sn) co-doped CoSb 3 at 623 K. • Extensive characterizations and computational results confirm both Sn and In as fillers prefer to occupy the interstitial sites in the CoSb 3 lattice. • The Fermi level moved into the conduction bands and increase of the density of state after doping, resulting in the increase power factor. • Young modulus and hardness of co-doped sample enhanced after Ag and Sn doping, indicating its potential for applying to miniature thermoelectric devices. Owing to the unique features, such as mechanically robust, low-toxic, high stability, and high thermoelectric performance, CoSb 3 -based skutterudite materials are among art-of-the state thermoelectric candidates. In this work, we develop a facile in-situ method for the growth of well-crystallinity (Ag, Sn) co-doped CoSb 3 thin films. This preparation method can efficiently control the dopant concentration and distribution in the thin films. Both the density functional theory calculation and the experimental results suggest that Sn and Ag dopants trend to enter the lattice and preferentially fill interstitial sites. Additionally, band structure calculation results suggest that the Fermi level moves into the conduction bands due to co-doping and eventually induces the increased electrical conductivity, which agrees with the optimization of carrier concentration. Moreover, an increase in the density of state after co-doping is responsible for the increased Seebeck coefficient. As a result, the power factors of (Ag, Sn) co-doped CoSb 3 thin films are greatly enhanced, and the maximum power factor achieves over 0.3 mW m −1 K −2 at 623 K, which is almost two times than that of the un-doped CoSb 3 film. Multiple microstructures, including Sb vacancies and Ag/Sn interstitial atoms as point defects, and a high density of lattice distortions coupled with nano-sized Ag-rich grains, lead to all scale phonon scatterings. As a result, a reduced thermal conductivity of ~0.28 W m −1 K −1 and a maximum ZT of ~0.52 at 623 K are obtained from (Ag, Sn) co-doped CoSb 3 thin films. This study indicates our facile in-situ growth can be used to develop high-performance dual doped CoSb 3 thins . The well-crystallized (Ag, Sn) co-doped thermoelectric thin films have been synthesized by a facial in-situ growth process and a high ZT of ~0.52 is achieved by rational band engineering and structural manipulations.