Transfer hydrogenation (TH) with in situ generated hydrogen donor is of great importance in reduction reactions, and an alternative strategy to traditional hydrogenation processes involving pressurized molecular hydrogen. Ammonia borane (NH3BH3, AB) is a promising material of hydrogen storage, and it has attracted much attention in reductive organic transformations owing to its high activity, good atom economy, non-toxicity, sustainability, and ease of transport and storage. This review focuses on summarizing the recent progress of AB-mediated TH reactions of diverse substrates including nitro compounds, nitriles, imines, alkenes, alkynes, carbonyl compounds (ketones and aldehydes), carbon dioxide, and N- and O-heterocycles. Syntheses protocols (metal-containing and metal-free), the effect of reaction parameters, product distribution, and variation of reactivity are surveyed, and the mechanism of each reaction involving the action mode of AB as well as structure-activity relationships is discussed in detail. Finally, perspectives are presented to highlight the challenges and opportunities for AB-enabled TH reactions of unsaturated compounds.