The characterizations of prepared low-molecular-weight polyhydroxybutyrate (LMWPHB) and the properties of LMWPHB photopolymerized with hydrophilic and hydrophobic acrylic monomers were studied with 1H-NMR spectroscopy, Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy, Instron tensile testing, and biodegradation tests. The results of 1H-NMR and FTIR spectroscopy confirmed that the prepared LMWPHB had transformed unsaturated ends that were photoreactive under UV light. The tensile strengths of the LMWPHB/acrylates decreased with increasing content of the added biodegradable LMWPHB because of the relatively long chains and large equivalent molar weights of LMWPHB. However, the flexibility of LMWPHB/acrylates changed differently with the type of acrylic monomer used. The LMWPHB/hydrophilic acrylate had a much more rapid biodegradation rate than the LMWPHB/hydrophobic acrylate because of the fast penetration of microorganisms. We demonstrated that the prepared LMWPHB could be used to control the biodegradation properties of acrylates and then could potentially be applied in biomedical fields. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 39501.