Nanoporous poly(cyclohexylethylene) (PCHE) monoliths were prepared from ordered poly(cyclohexylethylene)-polylactide (PCHE-PLA) diblock copolymers. The copolymers were prepared by first the catalytic hydrogenation of hydroxyl end-functionalized polystyrene (PSOH) giving hydroxyl end-functionalized PCHEOH. The hydroxyl functionality was utilized to form a metal alkoxide macroinitiator which catalyzed the polymerization of D,L-lactide. The resultant PCHE-PLA block copolymers were characterized by differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS), and Theological analysis. The Flory-Huggins interaction parameter, χ (estimated from rheological, SAXS, and solubility parameter data), was approximated to be 3 times that of the corresponding PS-PLA material. PCHE-PLA block copolymers containing PLA cylinders were degraded under basic conditions to remove the PLA. The resulting nanoporous monoliths showed increased thermal stability by SAXS and DSC and improved solvent resistance over nanoporous PS. These robust properties make nanoporous PCHE very desirable as a template for the synthesis of nanomaterials.