Polyesters based on polyols have emerged as promising biomaterials for various biomedical applications, such as tissue engineering and drug delivery systems, due to their biocompatibility, biodegradability, and versatile physicochemical properties.

As a glycerol-based polyester, poly(glycerol azelaic acid) (PGAz) has shown great potential for biomedical applications, such as tissue engineering. However, it tends to show low mechanical strength and a relatively fast biodegradation rate, limiting its capability of mimicking and supporting a broad range of hard tissues such as bone. Moreover, the typical thermal curing process of poly(glycerol-co-diacids) is one of their drawbacks. To overcome these limitations, glycidyl methacrylate (GMA) moieties were first grafted on the backbone of PGAz herein to achieve a UV-curable PGAz-g-GMA (PGAG) resin. Then polyvinylidene fluoride (PVDF), nano-hydroxyapatite, and Cloisite Na⁺ nanoclay were used to fabricate photo-crosslinked PGAG/PVDF nanocomposites with efficient properties to mimic various hard tissues. Our results demonstrated that all nanocomposites possessed a semi-crystalline structure with noticeable PVDF β-phase fraction. The scaffolds yielded Young's modulus, ultimate tensile strength, and elongation at break of 15–24 MPa, 13–15 MPa, and 50–65%, respectively that could meet the requirements for supporting cancellous bone tissue. The presence of nanofillers improved the hydrophilicity and slightly accelerated the biodegradation rate of the scaffolds. Additionally, it was illustrated that the scaffolds had no noticeable in vitro cytotoxicity, and mouse fibroblast L929 cells and osteoblast MG-63 cells attached to and proliferated on their surface desirably. Our findings indicate that the PGAG/PVDF blend and its nanocomposites could be high-potential candidates for a range of hard tissues, specifically cancellous bones.