Efficient synthetic access to highly functionalized 3,4-cyclohexane-annelated coumarins has been achieved by combining two methods. First, the important intermediates multisubstituted cyclic β-keto esters were prepared conveniently by condensing a variety of benzaldehydes with ethyl acetoacetate. A series of highly functionalized 3,4-cyclohexane-annelated coumarins were then synthesized by Amberlyst-15-catalyzed Pechmann condensation of multisubstituted cyclic β-keto esters with phenols. This synthetic method has the advantages of mild reaction conditions, good tolerance of a variety of functional groups, and satisfactory yields.