A La(OTf)3‐catalyzed domino method has been developed to synthesize the cis‐1,4‐benzoxazine derivatives from 2‐furylcarbinols 1 and o‐aminophenol derivatives, by a Piancatelli/C–N coupling/Michael addition process. A wide array of substrates could be used to give the desired products in good yields. Since this method involves simple reaction conditions and short reaction times, and has a broad substrate scope, it is particularly attractive for the efficient development of libraries of biologically relevant 1,4‐benzoxazine derivatives. Furthermore, a similar strategy was also successfully applied to form 1,2,3,4‐tetrahydroquinoxaline derivatives from 1 and N‐substituted o‐diaminobenzenes. A La(OTf)3‐catalyzed domino method has been developed to synthesize the cis‐1,4‐benzoxazine derivatives by a Piancatelli/C–N coupling/Michael addition process. A similar strategy was used to form 1,2,3,4‐tetrahydroquinoxaline derivatives from 1 and N‐substituted o‐diaminobenzenes. This method should be valuable for the construction of heterocycles with biological and medicinal activities.