The cycloaddition of CO2 with cyclohexene oxide is a promising method to convert CO2 into value-added products, such as cyclohexane carbonate, which may contribute to reducing greenhouse gas emissions. However, the process often relies on expensive, non-recoverable homogeneous catalysts. This study explores Zn-Zr-Al heterogeneous catalysts derived from layered double hydroxides synthesized via co-precipitation. The Zn/Zr molar ratio significantly influenced the physicochemical properties of the catalysts, including crystallite size, surface area, CO2 adsorption capacity, and surface carbonate species. Higher Zr content increased surface area, microporosity, and CO2 capture, correlating with catalytic performance. Under solvent-free conditions (50 bar CO2, 70 °C, 24 h), experiments without a cocatalyst achieved low conversions (<20%). Adding TBAB as a cocatalyst improved conversion to ~40%. Optimal performance was observed for a Zn/Zr ratio of 3, yielding conversions of 88.8%–97.6% and selectivities of 95.8%–96.1% as the temperature increased from 85 °C to 100 °C. Pressure enhancements (10–30 bar) further boosted conversion from 78.8% to 97.2%, with selectivities reaching 97.1%. The catalyst demonstrated good reusability, maintaining conversions of 94.3%–96.2% and selectivities of 94.6%–95.9% over three cycles. These results highlight the potential of Zn-Zr-Al catalysts as stable, reusable, and environmentally friendly systems for CO2 cycloaddition under mild conditions.