A variety of substituted derivatives of thiophene and 2-aminothiophene bearing o-acylphenol moieties were obtained via the reaction between 3-formylchromone with phenacyl thiocyanate in the presence of Et3N. This metal-free procedure for the synthesis of thiophene skeletons revealed a good efficiency, higher diversity, and wide substrate tolerance. These compounds have structural similarities to biologically active compounds reported in the literature. Besides, they can be used as a suitable candidate for the synthesis of fused-thiophene heterocycles through C–H activation processes.