The　physical　and　chemical　properties　of　gold　nanoparticles　can　significantly　influence　their　anti-tumor　efficacy.　Streamlining　synthesis　methods　to　modulate　these　properties　and　enhance　therapeutic　effects　could　facilitate　their　translation　into　clinical　applications.　This　study　presents　a　new　approach　to　synthesize　small　alkynylmodified　gold　nanoparticles　(Alk-GNP)　at　room　temperature　using　sodium　citrate　and　propiolic　acid　(PA)　to　reduce　chloroauric　acid.　The　resulting　Alk-GNP,　approximately　11　nm　in　size　with　narrow　dispersion,　contrasts　with　larger　gold　nanoparticles　(GNP)　synthesized　by　the　classical　Turkevich　method　using　boiling　water.　Subsequently,　a　round　composite　(CHAM)　was　developed　using　chitosan　and　hyaluronic　acid　to　co-deliver　Alk-GNP　and　the　photosensitizer　methylene　blue　for　synergistic　treatment.　CHAM　showed　excellent　stability　and　strong　CD44-positive　tumor　targeting　capabilities.　It　significantly　boosted　photothermal　activity　and　reactive　oxygen　species　generation　compared　to　current　GNP-based　formulations.　In　tumor-bearing　mouse　models,　CHAM　effectively　localized　in　tumor　tissue　and　exhibited　potent　photothermal　and　photodynamic　therapeutic　effects　to　inhibit　tumor　growth　while　ensuring　safety.　The　robust　data　presented　in　this　study　supports　the　potential　translation　of　this　approach,　offering　a　simplified　preparation　process　and　improved　tumor　treatment　efficacy.