A novel approach to skipped dienes has been developed through the TMSOTf-mediated one-pot addition–substitution of olefins 2a, 2f and 2g with imines 1a–1g, and a series of aryl substituted skipped dienes 3aa–3gf were accordingly obtained in 62%–94% yields. Moreover, semicyclic N,O-acetals 5 and 7 could also undergo this transformation to produce the corresponding skipped dienes 6aa and 6af–6al and 8ba and 8bf–8bk in moderate to good yields.