This review provides a comprehensive view of the application of first-row transition metals in asymmetric hydrogenation and asymmetric transfer hydrogenation. The catalytic behavior of 3d metals is significantly different from that of 4d and 5d metals. The replacement of noble metals with first-row transition metals has encountered challenges such as different reaction mechanisms and unexpected deactivation of the catalyst. The potential involvement of a single-electron process has been the most notorious feature of first-row metals. This review aims to give readers a picture of how first-row transition metals catalyze hydrogenation reactions and the corresponding enantioinduction models. Although this article is partitioned according to the substrate type, it is mechanism-oriented and is focused on catalytic systems. A certain catalytic system could be applied in the hydrogenation of different types of double bonds. Similarities within first-row metals and differences from their 4d and 5d congeners were emphasized.