In an effort to synthesize cobalt-rich metallaheteroboranes from decaborane(14) analogues, we have studied the reaction of 10-vertex nido-[(Cp*Co)2B6H6E2] (Cp* = η5-C5Me5, 1: E = Se and 2: E = Te) with [Co2(CO)8] under thermolytic conditions. All of these reactions yielded face-fused clusters, [(Cp*Co)2B6H6E2{Co(CO)}(μ-CO){Co3(CO)6}] (3: E = Se and 4: E = Te). Further, when clusters 3 and 4 were treated with [Co2(CO)8], they underwent further cluster buildup reactions leading to the formation of 16-vertex doubly face-fused clusters [(Cp*Co)2B6H6E2{Co2(CO)2}(μ-CO)2{Co4(CO)8}] (5: E = Se and 6: E = Te). Cobaltaheteroboranes 3 and 4 comprise one icosahedron {Co4B6E2} and one square pyramidal {Co3B2} moiety, whereas 5 and 6 are made with one icosahedron {Co4B6E2} and two square pyramidal {Co3B2} cores. In an attempt to generate heterometallic metal-rich clusters, we have explored the reactivity of decaborane(14) analogue nido-[(Cp*Co)2B7TeH9] (7) with [Ru3(CO)12] at 80 °C, which afforded face-fused 13-vertex cluster [(Cp*Co)2B7H7Te{Ru3(CO)8}] (8). Cluster 8 is a rare example of a metal-rich metallaheteroborane in which one icosahedron {Co2Ru2B7Te} and a tetrahedron {Ru2B2} units are fused through a common {RuB2} triangular face. Further, the treatment of nido-[(Cp*Co)2B6S2H4(CH2S2)] (9) with [Fe2(CO)9] afforded 11-vertex nido-[(Cp*Co)2B6S2H4(CH2S2){Fe(CO)3}] (10). The core structure of 10 is similar to that of [C2B9H11]2- with a five-membered pentahapto coordinating face. All of the synthesized metal-rich metallaheteroboranes have been characterized by multinuclear nuclear magnetic resonance (NMR) spectroscopy, IR spectroscopy, ESI-MS, and structurally solved by single-crystal X-ray diffraction analysis. Furthermore, theoretical investigations gave insight into the bonding of such higher-nuclearity clusters containing heavier chalcogen atoms.