Structural design, doping, and construction of heterojunctions are effective strategies for producing highly efficient photocatalytic materials. Herein, N-doped TiO2 was formed on hexagonal C3N4 tube through in-situ hydrolysis of a Ti source on a supramolecular precursor, followed by thermal treatment. As a result, a double-shell microtube, C3N4@TiO2 heterostructure was fabricated. It was worth noting that the supramolecular precursor was prepared from melamine and cyanuric acid, which not only served as a template for the double-shell tubular structure, but also provided nitrogen for the doping of TiO2. The photocatalytic efficiency of C3N4 @TiO2 was investigated by conducting hydrogen production experiments. The hydrogen production rate of C3N4@TiO2 was measured to be 10.1 mmol h(-1) g(-1), which is 4 times and 15 times that of C3N4 and TiO2, respectively. The improved photocatalytic activity of C3N4@TiO2 can be ascribed to (1) the tubular structure that provides a large number of reaction sites and enhances mass transport, (2) the heterojunction that is beneficial to charge separation, and (3) doping of TiO2 with nitrogen which extends its optical absorption range to visible light. This work demonstrates a facile method for synthesizing a highly efficient photocatalyst towards hydrogen evolution by modifying its structure and chemical composition as well as forming a heterojunction. (C) 2020 Elsevier Inc. All rights reserved.