Herein, gelated thermoresponsive large-compound vesicles (LCVs) are reported for the first time. The LCVs are prepared by self-assembly of poly(ethylene oxide)-block-poly[N-isopropylacrylamide-random-3-(trimethoxysilyl)propyl methacrylate] [PEO-b-P(NIPAM-r-TMPM)] in DMF-water mixture. Then, sol-gel reaction of the reactive PTMPM block is performed to stabilize the LCVs. LCVs with higher cross-linking density keep almost the same size under different temperatures while LCVs with lower cross-linking density display obviously thermoresponsive size transition between 22 and 36 degrees C. The gelated LCVs exhibit enhanced permeability with temperature elevation and their permeabilities at different temperatures all elevate with increasing the cross-linking density.