The growing demand for sustainable aviation fuels (SAFs) has driven interest in biomass-derived fuel precursors. This study investigates the aldol condensation of furfural and cyclopentanone (CP) over a series of Ce-modified zeolites and mesoporous catalysts to produce 2-(2-furylmethylidene) CP (FC) and its dimer 2,5-bis(2-furylmethylidene) CP (F2C), both relevant as SAF intermediates. A range of Ce-based materials, including Ce–H–Y-80, Ce-MCM-41, Ce-SBA-15, and Ce–H-Beta with varying Si/Al ratios, were synthesized and tested under specific reaction conditions. Catalyst characterization revealed distinct differences in surface area, acidity, basicity, and pore architecture, all contributing to the performance. Ce-MCM-41 exhibited the highest selectivity to FC (57%) at 65% conversion, linked to its mesoporosity and balanced acid–base properties. To further assess this catalyst’s performance, additional kinetic studies and reaction modeling were conducted, along with extended characterization of the spent and regenerated catalyst to evaluate stability and reusability. Zeolitic Ce–H–Beta catalysts demonstrated strong Brønsted acidity and delivered high conversion with moderate selectivity. A mechanistic correlation between acidity/basicity and activity was supported by the literature data. These findings highlight the potential of Ce-based heterogeneous catalysts in upgrading biomass-derived compounds into SAF precursors and support further development of regenerable, multifunctional catalytic materials.