The addition of a B-H bond to an unsaturated bond (polarized or unpolarized) is a powerful and atom-economic tool for the synthesis of organoboranes. In recent years, s-block organometallics have appeared as alternative catalysts to transition-metal complexes, which traditionally catalyze the hydroboration of unsaturated bonds. Because of the recent and rapid development in the field of hydroboration of unsaturated bonds catalyzed by alkali (Li, Na, K) and alkaline earth (Mg, Ca, Sr, Ba) metals, we provide a detailed and updated comprehensive review that covers the synthesis, reactivity, and application of s-block metal catalysts in the hydroboration of polarized as well as unsaturated carbon-carbon bonds. Moreover, we describe the main reaction mechanisms, providing valuable insight into the reactivity of the s-block metal catalysts. Finally, we compare these s-block metal complexes with other redox-neutral catalytic systems based on p-block metals including aluminum complexes and f-block metal complexes of lanthanides and early actinides. In this review, we aim to provide a comprehensive, authoritative, and critical assessment of the state of the art within this highly interesting research area.