Up to the present date, DFT methodology was employed to explore the explicit pathway and substrate-catalyst binding mode of the Ritter-type solvolysis reaction catalysed by XBbased CAT3 and CAT9. The investigation revealed that both catalytic systems strongly favour Pathway 1, suggesting that the XB-donor engages in NCIs with the R-X leaving group, initiating a heterolytic bond cleavage process, followed by an acetonitrile N-terminal attack. Notably, CAT3 and CAT9 exhibit distinct substrate binding modes: CAT3 adopts a bidentate binding mode, whereas CAT9 demonstrates a clear energetic preference for the monodentate mode, facilitated by secondary NCIs between the catalyst and the substrate. Despite these different binding modes, a direct comparison of the catalytic efficiency of CAT3 and CAT9 in the halide abstraction reaction reveals remarkably similar activities, a conclusion supported by both experimental sources and theoretical data.