This chapter explores the synergistic integration of organocatalysis and transition metal catalysis in enantioselective organic synthesis, focusing on chiral metal complexes that function as “organocatalysts in disguise.” These hybrid systems leverage the structural and electronic properties of metal ions to organize ligands into well-defined chiral environments, enabling precise stereocontrol through hydrogen bonding, phase-transfer mechanisms, and Brønsted acid/base interactions. Key examples include cobalt(III), iridium(III), ruthenium(II), zinc(II), and copper(II) complexes, which catalyze diverse asymmetric transformations such as Michael additions, α-aminations, Friedel–Crafts alkylations, and photocycloadditions. The metal center acts as a template to spatially arrange catalytic moieties, enhance ligand acidity, and provide metal-centered chirality, often achieving high enantioselectivity at low catalyst loadings. The chapter also highlights bifunctional catalysts that combine activation modes (e.g. enamine/hydrogen-bond donor (HBD) or photoactivated systems) and discusses challenges in traditional organocatalysis, such as limited stereocontrol and sensitivity to environmental conditions. Future perspectives emphasize the untapped potential of σ-hole-donating ligands (halogen/chalcogen bonds) to further expand the scope of metal-templated organocatalysis. This approach bridges coordination chemistry and organocatalysis, offering sustainable and efficient strategies for synthesizing chiral molecules in pharmaceuticals and fine chemicals.