A first example of solvent-and additive-free 1, 4-addition reaction of α, β-unsaturated ketones such as chalcones, 3-nonen-2-one and benzalacetone with trimethylsilyl cyanide (TMSCN) is described. The addition of TMSCN to chalcones, 3-nonen-2-one, and benzalacetone under microwave irradiation in the absence of Lewis or Brønsted acids and solvents, yielded the corresponding β-cyanoketones in good to moderate yields, as quite rapidly as in 5min. ...