A variety of slightly cross-linked poly(2-vinylpyridine)-poly(N-isopropylacrylamide) (P2VP-PNIPAM) core-shell microgels with pH- and temperature-responsive characteristic were prepared via seeded emulsion polymerization. Negatively charged sodium 2,6-naphthalenedisulfonate (2,6-NDS) could be internalized into the inner core, followed by formation of (P2VPH(+)/SO32-) supramolecular complex through the electrostatic attractive interaction in acid condition. The thermoresponsive characteristic feature of the (P2VPH(+)/SO32)-PNIPAM core-shell microgels was investigated by laser light scattering and UV-vis measurement, revealing an integration of upper critical solution temperature (UCST) and lower critical solution temperature (LCST) behaviors in the temperature range of 20-55 degrees C. The UCST performance arised from the compromised electrostatic attractive interaction between P2VPH(+) and 2,6-NDS at elevated temperatures, while the subsequent LCST transition is correlated to the thermo-induced collapse of PNIPAM shells. The controlled release of 2,6-NDS was monitored by static fluorescence spectra as a function of temperature change. Moreover, stopped-flow equipped with a temperature-jump accessory was then employed to assess the dynamic process, suggesting a millisecond characteristic relaxation time of the 2,6-NDS diffusion process. Interestingly, the characteristic relaxation time is independent of the shell cross-link density, whereas it was significantly affected by shell thickness. We believe that these dual therrnoresponsive core-shell microgels with thermotunable volume phase transition may augur promising applications in the fields of polymer science and materials, particularly for temperature-triggered release.