Kempe et al. and Milstein et al. have recently advanced the dehydrogenative coupling methodology to synthesize pyrroles from secondary alcohols (e.g., 3) and β-amino alcohols (e.g., 4), using PNP-Ir (1) and PNN-Ru (2) pincer complexes, respectively. We herein present a DFT study to characterize the catalytic mechanism of these reactions. After precatalyst activation to give active 1A/2A, the transformation proceeds via four stages: 1A/2A-catalyzed alcohol (3) dehydrogenation to give ketone (11), base-facilitated C-N coupling of 11 and 4 to form an imine-alcohol intermediate (18), base-promoted cyclization of 18, and catalyst regeneration via H2 release from 1R/2R. For alcohol dehydrogenations, the bifunctional double hydrogen-transfer pathway is more favorable than that via β-hydride elimination. Generally, proton-transfer (H-transfer) shuttles facilitate various H-transfer processes in both systems. Notwithstanding, H-transfer shuttles play a much more crucial role in the PNP-Ir system than in the PNN-Ru system. Without H-transfer shuttles, the key barriers up to 45.9 kcal/mol in PNP-Ir system are too high to be accessible, while the corresponding barriers (<32.0 kcal/mol) in PNN-Ru system are not unreachable. Another significant difference between the two systems is that the addition of alcohol to 1A giving an alkoxo complex is endergonic by 8.1 kcal/mol, whereas the addition to 2A is exergonic by 8.9 kcal/mol. The thermodynamic difference could be the main reason for PNP-Ir system requiring lower catalyst loading than the PNN-Ru system. We discuss how the differences are resulted in terms of electronic and geometric structures of the catalysts and how to use the features in catalyst development.