A simple route is reported to synthesize colloidal particle clusters (CPCs) from self-assembly of in situ poly(vinylidene fluoride)/poly(styrene-co-tert-butyl acrylate) [PVDF/P(St-co-tBA)] Janus particles through one-pot seeded emulsion single electron transfer radical polymerization. In the in situ Pickering-like emulsion polymerization, the tBA/St/PVDF feed ratio and polymerization temperature are important for the formation of well-defined CPCs. When the tBA/St/PVDF feed ratio is 0.75 g/2.5 g/0.5 g and the reaction temperature is 35 °C, relatively uniform raspberry-like CPCs are obtained. The hydrophobicity of the P(St-co-tBA) domains and the affinity of PVDF to the aqueous environment are considered to be the driving force for the self-assembly of the in situ formed PVDF/P(St-co-tBA) Janus particles. The resultant raspberry-like CPCs with PVDF particles protruding outward may be promising for superhydrophobic smart coatings.

Front Cover: Raspberry‐like colloidal particle clusters from self‐assembled poly(vinylidene fluoride)/poly(styrene‐co‐tert‐butyl acrylate) [PVDF/P(St‐co‐tBA)] Janus particles are synthesized via facile one‐pot seeded Pickering‐like emulsion polymerization via the single‐electron transfer mechanism. The driving force for such a self‐assembly is attributed to the higher hydrophobicity of the P(St‐co‐tBA) bulges on the Janus particles. These complex colloidal particle clusters are promising for superhydrophobic smart coatings with self‐cleaning properties, like lotus leaves. Further details can be found in the article by J. Yuan, W. Zhao, M. Pan,* and L. Zhu* on page 1282.