Heterobimetallic compounds continue to be vital in synthetic and materials chemistry due to the unique chemical properties of these species in comparison to their homometallic components. Investigations on mixed-metal alkali and alkaline earth metals are extensive for magnesium but the coordination chemistry and potential applications of the corresponding heavy alkaline earth metal have yet to be explored. The preparation of these species remains a challenge due to limited available synthetic strategies, and suitable ligand and solvent system. We are interested in the development of simple synthetic pathways to prepare this new class of compounds while exploring their structures and functions. Utilization of elevated temperature reactions and sterically demanding aryloxide provided access to the structurally novel heavy alkaline earth metal complexes. Here we present the synthesis and structures of alkali-heavy alkaline earth heterobimetallic complexes of the type [M_nAe(Odpp)_2+n] (M = Li, Na or K; Ae = Ca, Sr or Ba; Odpp = 2,6-diphenylphenol). Preliminary thermal studies of these compounds will also be discussed.