The tail-to-tail cross-dimerization of methyl methacrylate (MMA)/methacrylonitrile (MAN) with acrylates has been realized for the first time by an N-heterocyclic carbene organocatalysis to produce new difunctional compounds, four 2-methylhex-2-enedioates and three 5-cyanohex-4-enoates, in moderate to good isolated yields. The high selectivity was achieved by the dropwise addition of acrylates, leading to the selective Michael addition of the stable deoxy-Breslow intermediates to acrylates.