Biodegradable block copolymers containing poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and poly (${varepsilon}$-caprolactone) (PCL) units (PHCLs) with different contents of PCL block were synthesized successfully by using telechelic hydroxylated PHBV (PHBV-diol) with low molecular weight as a macroinitiator to initiate ring-opening bulk polymerization of ${varepsilon}$-caprolactone (${varepsilon}$-CL). The chemical structure and molecular weight were characterized by $^1H$ NMR, FTIR and GPC. The PHBV and PCL blocks in PHCLs were miscible in amorphous state, and formed separate crystalline phases with lower crystallinity than corresponding homopolymers, which was characterized by DSC and WAXD. The results of TGA showed that PHCLs underwent a two-step thermal degradation process. The thermal degradation process of PCL blocks was significantly different from PCL homopolymers. The activation energies of thermal degradation of PCL blocks calculated by Horowitz and Metzger method were much higher than that of each step of thermal degradation of PCL homopolymers.