Passive daytime radiative cooling (PDRC) has drawn significant attention recently for electricity-free cooling. Porous polymers are attractive for PDRC since they have excellent performance and scalability. A fundamental question remaining is how PDRC performance depends on pore properties (e.g., radius, porosity), which is critical to guiding future structure designs. In this work, optical simulations are carried out to answer this question, and effects of pore size, porosity, and thickness are studied. We find that mixed nanopores (e.g., radii of 100 and 200 nm) have a much higher solar reflectance R̅ solar (0.951) than the single-sized pores (0.811) at a thickness of 300 μm. With an Al substrate underneath, R̅ solar, thermal emittance ε̅LWIR, and net cooling power P cool reach 0.980, 0.984, and 72 W/m2, respectively, under a semihumid atmospheric condition. These simulation results provide a guide for designing high-performance porous coating for PDRC applications.