In this study, a KRGDKK (Lys-Arg-Gly-Asp-Lys-Lys) peptide with a RGD sequence is utilized as a functional group to synthesize a novel thermo-sensitive hydrogel. The KRGDKK peptide prepared by a solid phase synthesis approach is coupled to the ends of a poly[(epsilon-caprolactone)-co-lactide]-poly(ethylene glycol)-poly[(epsilon-caprolactone)-co-lactide] (PCLA-PEG-PCLA) triblock copolymer to obtain peptide-PCLA-PEG-PCLA-peptide. The self-assembly behavior of both PCLA-PEG-PCLA and peptide-PCLA-PEG-PCLA-peptide copolymers in aqueous solution is investigated, and hydrogels prepared from PCLA-PEG-PCLA and peptide-PCLA-PEG-PCLA-peptide are also prepared. An in vitro cell viability study demonstrated that the peptide-PCLA-PEG-PCLA-peptide hydrogels do not exhibit an apparent cytotoxicity, which suggests that the hydrogels have promising potential as injectable drug-delivery systems. Furthermore, compared with the PCLA-PEG-PCLA hydrogels, the peptide-PCLA-PEG-PCLA-peptide hydrogels display improved mechanical properties because of hydrogen bonding between the amino groups of KRGDKK. An in vitro drug release study showed that the peptide-PCLA-PEG-PCLA-peptide hydrogels exhibit outstanding controlled release properties and the release of the drug could be sustained for more than a month without initial burst.