Grape　seed　wastes　are　a　rich　source　of　bioactive　polyphenols.　This　study　compares　the　recovery　efficiency　of　traditional　maceration　extraction　(ME)　with　modern　extraction　techniques　(ultrasound-assisted　extraction　(UAE),　microwave-assisted　extraction　(MAE),　and　accelerated　solvent　extraction　(ASE)),　revealing　the　selective　extraction　of　polyphenolic　compounds　by　different　methods.　UPLC-ESI-MS/MS　analysis　was　used　to　identify　and　quantify　24　polyphenols.　ASE　showed　the　highest　efficiency　for　phenolic　acids　(e.g.,　gallic　acid,　231.75　μg/g)　and　proanthocyanidins　(e.g.,　procyanidin　B1,　126.18　μg/g),　while　MAE　was　optimal　for　flavonoids　recovery　(e.g.,　myricetin,　41.52　μg/g).　Multivariate　chemometric　analysis　revealed　co-extraction　patterns　among　structurally　related　compounds　(e.g.,　flavan-3-ols　with　galloylated　derivatives),　linking　extraction　parameters　to　the　selectivity　of　polyphenols.　Integrating　UPLC-ESI-MS/MS　profiling　of　24　polyphenols,　we　suggest　that　MAE/ASE　is　most　suitable　for　antioxidant-rich　nutraceuticals,　while　ME　is　optimal　for　thermally　labile　pharmaceuticals.　This　study　provides　practical　strategies　for　the　sustainable　utilization　of　grape　seed　by-products,　offering　industry-specific　solutions　to　reduce　waste　and　improve　the　recovery　of　bioactive　compounds.　©　2025　Elsevier　Ltd