The catalytic hydrogenation of CO₂ into value-added hydrocarbons offers a promising route toward carbon-neutral chemical manufacturing yet achieving selective formation of light C₂⁺ products remain challenging because of the high thermodynamic stability of CO₂ and the difficulty of promoting C–C coupling. Here, we present an exsolution-engineered multicomponent catalyst derived from a strontium titanate ferrite (STF) perovskite that enables tuneable conversion of CO₂ to light hydrocarbons (C₂–C₅). By tailoring the B-site composition with Fe, Cu, and Ni, we selectively exsolve bi-and trimetallic nanoparticles under mild reducing conditions, generating strongly socketed metallic ensembles at the perovskite surface. These anchored nanostructures enhance hydrogen activation, facilitate CO₂ activation, and modulate hydrocarbon selectivity between olefinic and paraffinic products. The catalyst achieves 55% C₂⁺ selectivity within the hydrocarbon fraction at atmospheric pressure, highlighting the effectiveness of exsolution-driven active-site engineering under comparatively mild reaction conditions. Operando UV–Vis spectroscopy further reveals on-stream dynamic redox reversibility at the nanoparticle–perovskite interface, providing insight into the structure–function relationships governing activity and selectivity. This work establishes atomic scale exsolution design as a versatile strategy for tuning product selectivity in CO₂ hydrogenation and other complex catalytic reactions. It also provides a route to tunable catalyst architectures in which nanoparticle composition, metal–oxide coupling, and interfacial redox chemistry can be simultaneously engineered from the parent lattice.