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Hollow silica particles with mesoporous walls (see Figure) are synthesized from solution by co‐assembly of silica with cationic fluorinated surfactants. The particles resemble vesicles, but retain wall patterns, indicating that they do not form from silica‐coated bilayers but by the co‐assembly of silica with micelles. Stronger shearing during synthesis causes the particles to aggregate into elongated particles with multiple hollow chambers.