Cyanophosphates (CPs) can be easily prepared from either ketones or aldehydes, and their reaction with NaN-EtN·HCl results in the formation of azidotetrazoles. Under microwave irradiation, successive fragmentation of the azidotetrazoles generates alkylidene carbenes that undergo [1,2]-rearrangement and are transformed into homologous alkynes. Treatment of ketone-derived CPs with TMSN and BuSnO as catalyst in toluene at reflux directly yields the corresponding internal alkynes, whereas the reaction of aldehyde-derived CPs with NaN-EtN·HCl in THF at reflux or TMSN-BuSnO (cat.) in toluene at reflux provides homologous terminal alkynes in good yields. These reactions take place under neutral conditions and can be successfully extended to obtain alkynes that are not usually accessible from the corresponding carbonyl compounds by the Ohira-Bestmann or Shioiri procedures, which require basic conditions.