The term ‘divergent catalysis’ describes different catalytic chemical reactions that occur with the same substrates (reactants) under controllable conditions, especially using different catalysts. Various substrates were found to work with versatile reactivity under different catalytic conditions, resulting in the formation of different products. However, the examples of rationally designed divergent catalysis are still few. This review is focused on the achievements of divergent catalysis with the simplest substrates in the past decades. It includes divergent catalysis of one-component and two-component reactions with the same and simple reagents, ranging from carbon-carbon-forming pinacol coupling, benzoin condensation, Ullmann coupling, C-H homocoupling or activation, ring-closing metathesis, cyclization, Stetter reaction, Baylis-Hillman reaction, Friedel-Crafts reaction, C-H Heck coupling, 1,2-additon reaction and Michael addition, to the carbon-heteroatom bond-forming C-N cross coupling, hydroamination reaction, aza-Michael reaction, C-H oxidative amination, acetalization, and esterification.