Silanes are important in chemistry and material science. The self-redistribution of HSiCl3 is an industrial process to prepare SiH4, which is widely used in electronics and automobile industries. However, selective silane cross-redistribution to prepare advanced silanes is challenging. We now report an enthalpy-driven silane cross-redistribution to access bis-silanes that contain two different types of Si-H bonds in the same molecule. Compared with entropy-driven reactions, the enthalpy-driven reaction shows high regioselectivity, broad substrate scope (62 examples) and high atom economy. Our combined experimental and computational study indicates that the reaction proceeds through a Ni(0)-Ni(II)-Ni(IV) catalytic cycle.