Since their initial development in the early 1900’s, Grignard reagents have proven to be immensely useful and are among the most common organometallic reagents. The nature of the reagents in solution is complex and depends on substituents, solvent, concentration and temperature. Despite continuing questions about their solid state and solution composition and conformation, organomagnesium reagents find new applications continually. In contrast, little information about the heavier alkaline earth organometallic compounds RMX and R₂M (R = alkyl, aryl; M = Ca, Sr, Ba, X = halide) exists. High reactivity due to the predominantly ionic character of the metal‐ligand bond and increased lability complicates synthetic access. Recent interest in the organometallic chemistry of the alkaline earth metals calcium, strontium and barium has been sparked by the realization that heavy alkaline earth metal organometallics play unique roles in synthetic applications, such as polymerization initiators and as reagents to modify polymers. As a result, the organometallic chemistry of calcium, strontium and barium has received significant attention over the last few years. This article summarizes recent results in this emerging area of chemistry. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)