Herein, we propose a novel mechanistic model for NHC-mediated carbonyl umpolung which involves the formation of a carbanionic carbene Breslow intermediate (CCBI). We have demonstrated theoretically that this reactive intermediate can be formed by inserting an aldehyde into the C4-H position of an N-aryl-substituted imidazolium-derived NHC via the generation of an H-bonded ditopic carbanionic NHC (dcNHC). Our DFT study on benzoin condensation has revealed that the mechanism of polarity inversion proceeding through the CCBI may be more energetically favorable than the classical mechanism of umpolung that uses the C2 carbene position in NHC. The potential existence of the CCBI highlights the dynamic and adaptive nature of NHC-mediated organocatalysis, particularly in relation to carbonyl umpolung. This finding also sheds light on new pathways in organocatalytic transformations employing the ambident reactivity of NHC, which may be particularly attractive for reactions involving furanic aldehydes and sterically encumbered N-aryl-substituted carbenes.