We present a transition-metal-free and environmentally friendly method for the alkylation of C(sp3)-H bonds in methyl-substituted N-heteroarenes using alcohols, mediated by bathophenanthroline. This straightforward and practical protocol employs readily available alcohols as alkylating agents, affording the desired alkylated N-heteroarenes in good to excellent yields using a broad range of aliphatic, aromatic, and heteroaromatic alcohols. The method also exhibits broad compatibility with various substituted methyl-N-heteroarenes, affording C-alkylated products in moderate to good yields. Mechanistic investigations, including deuterium-labeling and intermediate analysis, confirm that the reaction proceeds via a borrowing-hydrogen (BH) pathway.