A novel zinc phthalocyanine (ZnPc) hierarchical nanostructure with hollow interior space has been successfully obtained by a facile ethylene glycol solvent–thermal synthetic route. The as-obtained products were characterized by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), IR spectrum, UV–vis spectrum, Brunauer–Emmett–Teller analysis and contact angle measurement. It was indicated that the ZnPc micro-rectangular tubes with hollow interior space were built from densely nanosheets with a thickness of about 20nm. The obtained ZnPc showed high visible photocatalytic property to degrade rhodamine B (RB), which could be ascribed to the contribution of hierarchical nanostructure, high crystallinity and super-hydrophobic property.