The present study reports on the development of composite gold nanoparticles (AuNPs)/polymersome formulations, based on pH-responsive biocompatible polymer vesicles integrating prefunctionalized AuNPs, doped with a hydrophobic model probe for improved multimodal drug delivery. The polymer vesicles were prepared from an amphiphilic pentablock terpolymer poly(ε-caprolactone)-b-poly(ethylene oxide)-b-poly(2-vinylpyridine)-b-poly(ethylene oxide)-b-poly(ε-caprolactone) (PCL-PEO-P2VP-PEO-PCL), consisting of a pH-sensitive and biodegradable P2VP/PCL membrane, surrounded by neutral hydrophilic PEO looping chains. Additionally, partial quaternization of the P2VP block has been performed to introduce cationic moieties. Water-dispersible AuNPs carrying a hydrophobic molecule were encapsulated in the hydrophilic aqueous lumen of the vesicles, and the release was monitored at pH conditions simulating physiological and tumor environments. The complex delivery of the cargos from these vesicles showed improved and controlled kinetics relative to the individual nanocarriers, which could be further tuned by pH and chemical modification of the membrane forming block.