Two types of rare five-membered aza-heterocycles, namely 3,3-disubstituted-3H-pyrroles and 5-hydroxypyrrolines, were synthesized from calcium carbide and available sec-alkyl (het)aryl ketoximes in the MOH/DMSO (M=Na, K) superbase systems. In contrast to the known procedures implemented with acetylene gas, the modified method is expedient and much safer that makes these intriguing aza-heterocycles accessible for any laboratory without facilities working with acetylene gas.