3D porous framework composed of exfoliated ultrathin nanosheets is a hot topic in the field of energy storage and conversion. A facile method to prepare 3D mesoporous C3N4 with few-layered nanosheets interconnected in large quantity via H(2)sO(4) intercalation and subsequent thermal treatment was described herein. The obtained thermally-exfoliated C3N4 (TE-C3N4) was thoroughly characterized by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectroscopy, atomic force microscopy (AFM), UV-Vis diffuse reflectance spectroscopy (DRS) and Brun auer-Emmett-Teller (BET) measurements. The detailed analysis indicated that TE-C3N4 possessed enlarged inter-layer space, enhanced UV-light adsorption and high specific surface area with 3D interconnected structure composed of ultrathin 2D nanosheets. Compared to bulk C3N4, TE-C3N4 showed an enhanced photocatalytic activity for photodegradation of Rhodamine B under UV-light irradiation and exhibited no significant loss of photocatalytic activity after 11 recycled runs. The pseudo-first reaction rate constant for TE-C3N4 was about four times higher than that for pure bulk-C3N4. The better photocatalytic performance could be attributed to more active catalytic sites, prolonged photo-excited carrier lifetime and shorted pathway of the carriers to the reaction sites. (C) 2016 Elsevier Inc. All rights reserved.