Solar semiconductor photocatalysis technology has been widely studied by researchers all over the world because of its green pollution-free, renewable and beneficial solution to global warming. Since the catalytic activities of semiconductor photocatalysts depend on their surface electron structures and atomic structures, which are strongly dependent on the crystal face, the catalytic activities of photocatalysts are significantly affected by the crystal surface exposed in the reaction process. In recent years, crystal facet tuning engineering has become a very important method of fine-tuning the physical and chemical properties of semiconductors. Tungsten trioxide (WO3) semiconductor catalyst is often used for photoanode in photoelectrochemical systems because of its good photocatalytic properties. In this paper, the recent progress of organic substances (organic small molecules and organic macromolecules) as structural inducers for the WO3 crystal structure regulation is reviewed, the mechanism and principle of the regulation of organic substances on crystal surface are introduced, looking for new experimental direction and breakthrough points, summarizing the current applications of WO3 photoelectrocatalysis in real life, such as solar water splitting, electrochromism, gas sensors, degradation of organic pollutants, etc. Finally, perspectives are given on the interesting research direction that may guide future studies.