This study reports on the adsorption (dehumidification)-desorption (humidification) behavior of cetylpyridinium bromide (CPB) coated starch particles (SPs), denoted as SP-CPB, as a potential desiccant material for air-to-air energy exchangers. CPB is a cationic surfactant with antibacterial activity that can be used to modify the surface properties of SPs, especially at variable CPB loading levels (SP-CPB0.5, SP-CPB2.5, and SP-CPB5.0, where the numeric suffix represents the synthetic loading level of CPB in mM). The SP-CPB0.5 sample displayed optimal surface area and pore structure properties that was selected for water sorption isotherm studies at 25 °C. The CPB-coated SPs sample (SP-CPB0.5) showed an improved water vapor uptake capacity compared to unmodified starch (SPs) and other desiccant systems such as high amylose starch (HAS15) and silica gel (SG13). Single-step and cyclic water vapor sorption tests were conducted using a small-scale exchanger coated with SP-CPB0.5. The calculated latent effectiveness values obtained from direct measurements using cyclic tests (65.4 ± 2%) agree closely with the estimated latent effectiveness from single-step tests (64.6 ± 2%) at controlled operating conditions. Compared to HAS15- and SG13-coated exchangers, the SP-CPB0.5-coated exchanger performed much better at controlled operating conditions, along with improved longevity due to the CPB surface coating. The presence of CPB did not attenuate the uptake properties of native SPs. Latent effectiveness of SP-CPB0.5-coated exchanger was enhanced (5-30% higher) over that of the SG13- or HAS15-coated exchangers, according to the wheel angular speed. This study reports on a novel and sustainable SP-CPB0.5 material as a promising desiccant coating with tunable uptake and surface properties with potential utility in air-to-air energy exchangers for ventilation systems.