Summary: Novel light‐sensitive hollow capsules were fabricated from the small molecule 3‐sulfopropylacrylate potassium (SPA) and poly(allylamine hydrochloride) (PAH). With UV irradiation, SPA could be photopolymerized in the wall of hollow capsules. After photopolymerization the capsule size and surfaces showed pronounced differences. The capsules became much more rigid as indicated by an increase in the modulus of more than a factor of 5.