Transfer hydrogenation (TH) has historically been dominated by Meerwein–Ponndorf–Verley (MPV) reactions. However, with growing interest in amine–boranes, not least ammonia–borane (H3N⋅BH3), as potential hydrogen storage materials, these compounds have also started to emerge as an alternative reagent in TH reactions. In this Review we discuss TH chemistry using H3N⋅BH3 and their analogues (amine–boranes and metal amidoboranes) as sacrificial hydrogen donors. Three distinct pathways were considered: 1) classical TH, 2) nonclassical TH, and 3) hydrogenation. Simple experimental mechanistic probes can be employed to distinguish which pathway is operating and computational analysis can corroborate or discount mechanisms. We find that the pathway in operation can be perturbed by changing the temperature, solvent, amine–borane, or even the substrate used in the system, and subsequently assignment of the mechanism can become nontrivial.