Most of the synthetic biodegradable polymers are hydrophobic and lack of bioactivity. In contrast, native polymers, such as starch are bioactive and hydrophilic, but starch alone cannot be processed easily. In this paper, the PLGA fibers were modified with starch using coaxial electrospinning to improve its hydrophilicity and biocompatibility. To observe the bioactivity changes of the composite fibers, the fibers were submerged in the SBF for one week. Meanwhile, degradation rate of fibers was tested in PBS. Results showed that the hydrophilicity and degradation rate of fibers were improved after adding starch into the PLGA fibers.