climate change. [1] Thus, there is an acute need to develop green technologies for converting solar energy into pure chemical energy that could reduce the greenhouse effect and alleviates the global energy crunch. [2] Photocatalytic CO 2 reduction into CO or economic hydrocarbon fuel like methane (CH 4 ), as well as photoelectrochemical water splitting into a zerocarbon emission fuel (H 2 production) are promising ways to convert and store solar energy. [2c,3] Semiconductor nanoparticles have gained interest in the fields of photocatalysis, water splitting, and energy conservation and conversion. [2b,3c,4] Among them, titanium oxide has played a significant role in efficiently mitigating air and water pollution problems due to its excellent optoelectronic properties and long-term photostability. [2c,4-7] Yet, the inappropriate large energy band gap, high electron-hole recombination, and unfavorably low solar light consumption have hindered the photoconversion efficiency of the pristine TiO 2 semiconductor. [2c,4b,8] Heterostructuring TiO 2 with an appropriate semiconductor is an operative approach to overcome its drawbacks and construct an efficient photocatalyst. [2c,4a,8] MoS 2 is an appealing semiconductor for fabricating heterostructured Regulating the transfer pathway of charge carriers in heterostructure photocatalysts is of great importance for selective CO 2 photoreduction. Herein, the charge transfer pathway and in turn the redox potential succeeded to regulate in 2D MoS 2 /1D TiO 2 heterostructure by varying the light wavelength range. Several in situ measurements and experiments confirm that charge transfer follows either an S-scheme mechanism under simulated solar irradiation or a heterojunction approach under visible light illumination, elucidating the switchable property of the MoS 2 /TiO 2 heterostructure. Replacing the simulated sunlight irradiation with the visible light illumination switches the photocatalytic CO 2 reduction product from CO to CH 4.13 CO 2 isotope labeling confirms that CO 2 is the source of carbon for CH 4 and CO products. The photo electrochemical H 2 generation further supports the switching property of MoS 2 /TiO 2 . Unlike previous studies, density functional theory calculations are used to investigate the band structure of Van der Waals MoS 2 /TiO 2 S scheme after contact, allowing to propose accurate charge transfer pathways, in which the theoretical results are well matched with the experimental results. This work opens the opportunity to develop photocatalysts with switchable charge transport and tunable redox potential for selective artificial photosynthesis.