An effective Pd(II)/Ag(I)‐promoted intramolecular cross‐dehydrogenative coupling (CDC) of substituted 1‐benzylimidazoles under air provides, for the first time, a simple access to several functionalized imidazo[2,1‐a]isoindoles, an interesting class of polycyclic heteroaromatic compounds. The direct involvement of two unactivated carbon–hydrogen bonds, without any directing group, grants an elevated atom economy of the whole process.