We report here the first example of cross-coupling between two different and unactivated C(aryl)-O bonds with chromium catalysis. The combination of a low-cost Cr(II) salt, 4,4'-di-tart-butyl-2,2'-dipyridyl (dtbpy) as the ligand, and magnesium as the reductant shows high reactivity in promoting the reductive cross-coupling of aryl methyl ether derivatives with aryl esters by cleavage and coupling of two different C(aryl)-O bonds under mild conditions. The formation of active low-valent Cr species by reduction of CrCl2 with Mg can be considered, which prefers to initially activate the C(aryl)-O bond of phenyl methyl ether with the chelation help of dtbpy and an o-imine auxiliary. The subsequent consecutive reduction, second C(aryl)-O activation, and reductive elimination allow for the achievement of selective cross-coupling of C(aryl)-O/C(aryl)-O bonds.