We herein disclose a new synthetic strategy for a diverse series of biologically interesting flavone‐coumarin molecular hybrids based on iron(III) triflate‐assisted direct and straightforward skeletal rearrangement of warfarin framework upon heating warfarin analogs in N, N‐dimethylformamide (DMF). Good yields, reasonable reaction time, broad substrate scope and tolerance of various functional groups, scalability, and operational simplicity are the key features of this newly developed method.