Exploring new and efficient cocatalysts to boost photocatalytic CO 2 reduction is of critical importance for solar-to-fuel conversion. As an emerging carbon allotrope, graphdiyne (GDY) features 2D characteristics and unique carboncarbon bonds. Herein, a novel GDY cocatalyst coupled TiO 2 nanofibers for boosted photocatalytic CO 2 reduction, synthesized by an electrostatic selfassembly approach is reported. First-principle calculation and in situ X-ray photoelectron spectroscopy measurement reveal that the delocalized electrons in GDY can hybrid with the empty orbitals in TiO 2 within the TiO 2 /GDY network, leading to the formation of an internal electric field at the interfaces, pointing from GDY to TiO 2 . The theoretical simulation further implies strong chemisorption and deformation of CO 2 molecules upon GDY, which can be verified by in situ diffuse reflectance infrared Fourier transform spectroscopy. These effects, in combination with the photothermal effect of GDY, result in enhanced charge separation and directed electron transfer, enhanced CO 2 adsorption and activation as well as accelerated catalytic reactions over the TiO 2 /GDY heterostructure, thereby resulting in significantly improved CO 2 photoreduction efficiency and meanwhile with remarkable selectivity. This work demonstrates that GYD can function as a highly effective cocatalyst for solar energy harvesting and may be used in other catalysis processes.The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/adfm.201904256. solar irradiation is recognized as a potential solution to these issues. [6][7][8][9][10][11] As one of the most popular photocatalytic materials, TiO 2 is chemically stable, nontoxic and earth-abundant to be proverbially utilized for CO 2 photoreduction. [12][13][14][15][16] However, the photocatalytic efficiency of unitary TiO 2 is still far away from the practical requirements largely due to its rapid electron-hole recombination. [17][18][19][20] Modifying TiO 2 with a cocatalyst has been widely adopted to tackle this issue owing to the advantages of cocatalysts such as improving the selectivity, minimizing the overpotentials, promoting the charge separation, enhancing the adsorption of CO 2 , suppressing the photocorrosion and so on. [21,22] Up to now, various cocatalysts have been exploited to promote the photocatalytic performance of TiO 2 and the most widely used cocatalysts were noble metals, such as Pt, Pd, Au, Ag, and their alloys. [23][24][25][26][27][28] However, noble metals are scarce and expensive, hindering their prospect severely. Therefore, it is of significance to search for novel cocatalysts for TiO 2 -based photocatalyst to improve the photocatalytic CO 2 reduction performance.Carbon allotropes such as 0D carbon dot, 1D carbon nanotube and 2D graphene have attracted significant interests in many fields including catalysis, new device structures and solar energy harvesting. [29][30][31] Particularly, the discovery of graphene has raised a wave of new ...