In this paper, nitrogen doped ZnO/Carbon hollow rhombic dodecahedral is successfully synthesized via an effective self-template way, which includes the synthesis of self-template Zn-based zeolitic imidazolate frameworks and then calcinations in nitrogen atmosphere. The as-synthesized nitrogen doped ZnO/Carbon hollow rhombic dodecahedral shows large specific surface area (534.1 m(2)g(-1)) and porous. In view of its unique structure, large specific surface area, porous and chemical compositions, applying as photoelectrochemical sensing material for determination glutathione, it demonstrates that the nitrogen doped ZnO/Carbon hollow rhombic dodecahedral produces a wide linear determination range (10-1200 mu M), high selectivity and low detection limit (8.0 mu M). Results in our work suggest that nitrogen doped ZnO/Carbon hollow rhombic dodecahedral is a promising photoelectrochemical sensing material for detection of glutathione. More importantly, the current synthesis route provides a simple and versatile method for preparation of nitrogen doped hollow structured materials deriving from metal-organic frameworks.