An effective directly modifying method to fabricate all-polymeric multiscale hierarchical particles (MHPs) is reported. The wettability of the MHP coatings could be readily tuned from hydrophobic (water contact angle, WCA, 128.6 ± 3°) to superhydrophobic (WCA, 171.2 ± 2°) by controlling the feed ratio of premixed 2-(perfluorooctyl)ethyl methacrylate/divinylbenzene (FOEMA/DVB) monomers without special equipment and extra modification. The building blocks for self-assembly colloidal coatings, poly(tert-butyl acrylate)@poly(4-tert-butyl styrene)-divinylbenzene-2-(perfluorooctyl)ethyl methacrylate (PtBA@PtBS-DVB-FOEMA) MHPs with tunable morphology, are prepared via in situcapping of fluorinated cross-linking networks onto MHP precursors (i.e., half-finished raspberry-like PtBA@PtBS particles) during the soap-free seeded emulsion polymerization (SSEP). The MHP microstructure could be conveniently regulated by changing the feed ratios of tBS/PtBA and FOEMA/DVB. The investigation results show that the chemical composition and surface roughness of the MHPs significantly affect the coatings’ wettability. The agile transition of the wettability could be ascribed to the thermodynamic driving process that the hydrophobic fluoroalkyl side chains in the cross-linking network always tend to stretch toward the bottom of the depressions on the MHP surface rather than the protrusions near the aqueous phase due to their intrinsic hydrophobicity.