By introducing UV-sensitive chemical groups causing different potential response as building blocks, fabricated LbL capsules can be endowed with dual UV-responsive properties in specific layers. One block is responsible for fast capsule sealing and the other for longer term capsule swelling and rupture. Therefore, the multifunction of these capsules could be activated selectively when exposed to external UV light with suitable wavelengths. In this work, dual-functional complex microcapsules (PDADMAC/PAZO)4-(DAR/Nafion)2 containing both diazonium and aozbenzene groups were proposed as clear examples to realize a time-dependent UV response for successive encapsulation and release. Upon exposure to UV light, the DAR/Nafion layers underwent a rapid in situ cross-linking and hence to seal the capsule shells through diazonium-related photolysis. Then further gradual shell swelling was followed by realignment of azobenzene molecules in PDADMAC/PAZO layers. Fluorescent polymers were consequently studied as cargo substances. Results indicated that continuous UV light triggered rapid cargo encapsulation over minutes time scale and gradual release with continuous irradiation over hours.