An efficient and concise approach for the synthesis of polysubstituted pyridines has been achieved through copper-catalyzed oxidative sp³ C–H coupling of oxime acetates with toluene derivatives. Besides, benzylamine and p-toluenesulfonylhydrazone were also introduced to react with oxime acetates to enrich the diversity of this synthetic method. These transformations provide highly flexible and facile preparation of substituted pyridines and thus are useful in practical synthesis.