The potential use of biomass co-combustion derived fly-ash products and zeolite 13X for the elimination of volatile organic compounds (VOCs) using ozone was investigated for an integrated solar-assisted air purification and desiccant cooling system. Fly-ash products from rice husk-coal co-combustion at different biomass blending ratios were used as the adsorbent/catalyst materials. The material characteristics of the adsorbent/catalyst materials such as metal content and surface area were compared and correlated with the catalytic activities. It was found that the surface area and the metal constitutes have made the catalytic activities over the fly-ash products from biomass co-combustion superior to that from coal-only combustion. The elevated reaction temperatures from 25°C to 75°C also have significant effects on the removal of VOCs. The apparent activation energies of the reaction path over the fly-ash products with the addition of ozone to the air were reduced, when compared with the use of air as an oxidant. On the other hand, the potential synergy to Zeolite 13X was explored. The combined catalytic ozonation and adsorption enhanced the VOCs removal and at the same time reduced the intermediates emission. Furthermore, the hydrophilic properties of zeolite 13X could be utilized to handle the latent load of the solar-assisted ventilation system for energy conservations.