We report a new simple method to access highly substituted cyclopentanes via Lewis acid-initiated formal [3 + 2]-cycloaddition of donor-acceptor cyclopropanes to 1,3-dienes. This process displays exceptional chemo- and regioselectivity as well as high diastereoselectivity, allowing for the synthesis of functionalized cyclopentanes and bicyclic cyclopentane-based structures in moderate to high yields. Moreover, one-pot synthesis of biologically relevant cyclopentafuranones, based on reaction of donor-acceptor cyclopropanes with dienes, has been developed.