The polyacrylonitrile (PAN)-iron octocarboxyphthalocyanine (FePc(COOH)8) nanofibers were prepared using electrospinning technique and introduced into the interlayer of a carboxymethyl cellulose (CMC)-polyvinyl alcohol (PVA)/chitosan (CS)-polyvinyl alcohol bipolar membrane (BPM), which was characterized using SEM, contact angle measurement, current-voltage characteristics, AC impedance spectroscopy and so on. The experimental results showed that after modification by PAN-FePc(COOH)8 nanofibers, the membrane impedance of the BPM and its cell voltage were decreased. That indicated that the water splitting efficiency in the interlayer of the BPM was increased. Then the prepared CMC-PVA/PAN-FePc(COOH)8/CS-PVA BPM was used in the electro-oxidized preparation of dialdehydle starch (DAS). The experimental results indicated that a current density of 20mA·cm-2 was suitable to obtain high current efficiency. When the electrolysis time was 3h at a current density of 20 mA·cm-2 , the current efficiency of the CMC-PVA/PAN-FePc(COOH)8/CS-PVA BPM-equipped cell was as high as 67%.