Organotellurium ligand-facilitated metal structures are known for their catalytic activity, anti-cancer activities, and nanomaterial applications. A wide range of organotellurium ligands, including telluroethers, pincer-based frameworks, and tellurolates, have been extensively explored for their coordination with diverse metal centers. These ligands have been successfully complexed with base metals, platinum group metals, rare earth elements, and representative metals, providing a unified resource of literature on metal complexes of organotellurium ligands. The resulting metal-organotellurium complexes exhibit intriguing structural diversities and potential applications in catalysis, materials science, and coordination chemistry. A comprehensive review on various applications of organotellurium ligands has not been available since 2005. Moreover, within the broader field of chalcogen chemistry, organotellurium ligands remain relatively less explored. Hence, this review focuses on the synthetic strategies and various applications of metal complexes containing organotellurium ligands, addressing a significant and critical gap existing in the literature. This review provides a comprehensive analysis of organotellurium ligands, focusing on their synthesis, structural diversity, and coordination chemistry. Beyond their fundamental significance, these ligands play a vital role in life sciences, nanochemistry, and materials science. Their catalytic proficiency is evident in essential organic reactions, including the Suzuki-Miyaura and Mizoroki-Heck couplings, alcohol oxidation, C-N bond formation, aldehyde activation, and nitrophenol reduction.