Innate immune responses recognizing pathogen associated molecular patterns (PAMPs) play a crucial role in adaptive immunity. Toll-like receptors (TLRs) and C-type lectin receptors (CLRs) contribute to antigen capture, uptake, presentation and activation of immune responses. In this contribution, metal-free reversible addition–fragmentation chain transfer (RAFT) polymerization of N-3,4-dihydroxybenzenethyl methacrylamide (DMA) and 2-(methacrylamido) glucopyranose (MAG) under sunlight irradiation using 2-cyanoprop-2-yl-α-dithionaphthalate (CPDN) as iniferter agent, can be employed to fabricate the multivalent glycopolymer containing bioresponsive sugar group and multifunctional catechol functionalities. The polymerization behavior is investigated and it presents controlled features. Moreover, bioinspired dopamine chemistry can be successfully utilized to form in situ glycopolymer-coated gold nanoparticles (AuNPs) without the need of additional reducing reagent, design “pathogen-mimetic” glycoadjuvant recognized by both CLRs and TLRs. The synthetic glycoadjuvant is found to enhance the adjuvant activity as “infected signals” in vitro.