Skew morphisms, which generalise automorphisms for groups, provide a fundamental tool for the study of regular Cayley maps and, more generally, for finite groups with a complementary factorisation $G=BY$, where $Y$ is cyclic and core-free in $G$. In this paper, we classify all examples in which $B$ is monolithic (meaning that it has a unique minimal normal subgroup, and that subgroup is not abelian) and core-free in $G$. As a consequence, we obtain a classification of all proper skew morphisms of finite non-abelian simple groups.