Herein, four chitooligosaccharide derivatives (COS-RA, COS-FA, COS-VA, COS-GA) were prepared by laccase-catalyzed chitooligosaccharide modification with rosmarinic acid (RA), ferulic acid (FA), gallic acid (GA), and vanillic acid (VA), and structures were characterized. RA and FA resulted in higher amino-substitution in the chitooligosaccharides than GA and VA. COS-RA and COS-FA had greater DPPH scavenging rates than COS-GA and COS-VA. Compared with COS treatment, spraying 250 mg L COS-RA or COS-VA 6 times (once per 7 days) increased soluble sugar and anthocyanin content by 18.6%-23.2% and 41.7%-46.7%, respectively, from the fruit expansion to harvest stage. COS-RA and COS-VA also enhanced gene expression related to anthocyanin synthesis ( and ) and monomeric anthocyanin accumulation (Mal-3-O-glu, Petu-3-O-ace-glu, Del-3-O-glu). Therefore, chitooligosaccharide derivatives may improve grape fruit anthocyanin accumulation by regulating antioxidant systems, improving the photosynthetic rate and inducing gene expression related to anthocyanin synthesis.