Abstract We have developed a simple K2S2O8‐mediated C‐H bond functionalization of 2‐phenyl pyridines (C‐2 position) with ethers involving C(sp2)‐C(sp3) cross‐dehydrogenative coupling. The reaction does not require metal catalysts nor visible light and operates under mild conditions. Furthermore, the protocol is easily scalable and extendable to a wide range of pyridine derivatives.