Thiophene-and furan-derived aminocarbene complexes are regioselectively lithiated by BuLi at position 5, while lithiated aminocarbenes containing pyrrole or phenyl groups can be obtained by a bromine to lithium exchange reaction using BuLi. Such prepared lithiated aminocarbene complexes react with alkyl halides, aldehydes, ketones, acyl chlorides, and DMF, giving high yields of functionalized aminocarbene complexes hardly accessible by other ways.