Methane (CH4) gas sensors play an important role in industrial safety and detection of indoor gas quality. In general, metal oxide semiconductor sensing materials with nano-structure have high responses to the target gas. However, the sensor resistance is usually very high. Considering the practical application, it is vital to reduce base resistance and improve sensitivity for gas sensors. Herein, Pd-doped SnO2 nanoparticles were prepared as the basis material by a simple sol-gel method. In order to adjust the resistance, the pentavalent metal element (Sb) was introduced via a simple doping route. As CH4 sensing layers, the prepared SnO2-sensors doped with Pd and Sb exhibited the most obvious resistance reduction effect. Meantime, excellent sensing performances including high response, fast response/recovery time, excellent reproducibility and great stability were also obtained. In-depth research has shown that the ability to reduce resistance depends on the effective internal doping of cation with high valence. The enhanced sensing capability can be attributed to the 'synergistic effects' including catalytic effects of novel metals, increased oxygen vacancies and decreased band gap energy. This work can provide a new opportunity to design metal oxide sensing materials with low resistance and high sensitivity.