A novel protocol of rhodium-catalyzed tandem C–H annulation of aldehyde and aniline with diazonaphthalen-1(2H)-one via transient directing group strategy and sequential nucleophilic substitution has been demonstrated in moderate to excellent yields. This reaction proceeds smoothly via intramolecular cyclization to form 6H-benzo[c]chromen-6-ol and is followed by nucleophilic substitution of para-carbon of aniline to construct 6-aryl-6H-benzo[c]chromene derivatives. A series of 6-aryl-6H-benzo[c]chromenes were synthesized in one-pot via the tandem C–H annulation.