Peripheral nerve injury (PNI) is a neurological disorder that causes more than 9 million patients to suffer from dysfunction of moving and sensing. Using biodegradable polymers to fabricate an artificial nerve conduit that replicates the environment of the extracellular matrix and guides neuron regeneration through the damaged sites has been researched for decades and has led to promising but primarily pre-clinical outcomes. However, few peripheral nerve conduits (PNCs) have been constructed from controllable biodegradable polymeric materials that can maintain their structural integrity or completely degrade during and after nerve regeneration respectively. In this work, a novel PNC candidate material was developed via the electrospinning of polyhydroxy butyrate/chitosan (PHB/CS) composite polymers. An SEM characterisation revealed the resultant PHB/CS nanofibres with 0, 1 and 2 wt/v% CS had less and smaller beads than the nanofibres at 3 wt/v% CS. The water contact angle (WCA) measurement demonstrated that the wettability of PHB/CS electrospun fibres was significantly improved by additional CS. Furthermore, both the thermogravimetric analysis (TGA) and differentiation scanning calorimetry (DSC) results showed that PHB/CS polymers can be blended in a single phase with a trifluoracetic solvent in all compositions. Besides, the reduction in the degradation temperature (from 286.9 to 229.9 °C) and crystallinity (from 81.0% to 52.1%) with increasing contents of CS were further proven. Moreover, we found that the degradability of the PHB/CS nanofibres subjected to different pH values rated in the order of acidic > alkaline > phosphate buffer solution (PBS). Based on these findings, it can be concluded that PHB/CS electrospun fibres with variable blending ratios may be used for designing PNCs with controlled biodegradability.