A transition metal-free synthesis of β-(pyridin-2-yl)-methyl ketones, using (pyridin-2-yl)methyl alcohols and ketones through the 2-pyridinylmethyl borrowing strategy, has been disclosed. This approach provides an efficient, available and environmentally benign access, leading to alkylation products with broad functional group tolerance and excellent yields. Meanwhile, the selective cleavage of unactivated C(sp³)–C(sp³) bonds of common secondary alcohols was achieved with high atom economy.