The preparation of 2,6-substituted piperidine derivatives through diastereoselective C-H functionalization of corresponding nitrogen heterocycles represents an appealing protocol and yet remains a formidable challenge. Here, we describe a stereochemically complementary oxidative C-H functionalization of N-carbamoyl tetrahydropyridines with a wide variety of building blocks, providing either the cis- or trans-2,6-substituted piperidines with diverse patterns of functionalities. The mild metal-free process exhibits excellent regio- and diastereoselectivities as well as functional group tolerance. The synthetic utilities in natural product and analogue syntheses are also described.