Porous polymeric material has emerged as promising choice for making passive daytime radiative cooling (PDRC) emitter. However, it is still an unmet challenge to establish a flexible method to achieve dynamic pore-formation for the purpose of studying the relationships between the porous structure and the resultant cooling performance. The current study reports a novel strategy to construct asymmetric multi-layered porous structure in situ within the matrix of pre-formed polystyrene coating. The modified procedure of inverse emulsion - breath figure method is adopted, and solvent-nonsolvent exchanging process is also involved during the pore-formation process, leading to the formation of hierarchical porous structure with rather high porosity. Geometrical features of the generated pores are effectively regulated by simple adjustment of the experimental parameters of the water ratio of the emulsion and the humidity. The relationship between the pore structure and optical & cooling properties has been established based on experimental facts. By tuning of optimal conditions, the in-situ pore-formation can endow the polymeric coating with high solar reflectance (∼85 %) and infrared emittance (∼98.4 %), resulting in passive temperature drop of 12 °C and cooling power of 91 W/m2. This study provides experimental information to get some insight into the designing principle of porous polymeric PDRC materials, and formulates unique strategy of in-situ functionalization via structural transformation upon polymeric objects or devices.