We report a detailed study that compares various composite materials (CM): Ag/ZnO, Ag/SnO2, Ag/C, Ag/WC, Ag/WC–C and Ag/Ni used in high-current dc circuit breaker applications. Their structural, mechanical, electrical and wetting properties were investigated. In parallel, switching operation tests on the same compounds were performed on commercial high-speed circuit breakers under real conditions (30 kA–900 V). A correlation between the microscopic variables and switching performances of the CMs was established. Materials like Ag/WC and Ag/WC–C were found to be unsuitable for the reliable functionality of the device. In contrast, Ag/C and Ag/SnO2 materials with high electrical and high thermal conductivity revealed remarkably good behaviour during switching operation tests.