Ongoing efforts to design novel materials with efficient structure‐property‐performance relations prove challenging. Core‐shell structures have emerged as novel materials with controlled production routes and highly tailorable properties that offer extensive advantages in advanced oxidation processing, particularly in photocatalysis and photoelectrochemical applications. WO3, which is an optoelectronically active semiconductor material, is a popular material in current studies in the field of photo(electro)catalysis. Considerable progress has been made using core‐shell WO3 architectures, which warrants an evaluation in terms of processing and preparedness for their use in versatile catalytic and energy storage applications. This paper presents an in‐depth assessment of core‐shell WO3 architectures by highlighting the design challenges and protocols in powder and thin‐film chemical processing. The development of specific core‐shell designs for use in targeted applications, such as H2 production, CO2 reduction, wastewater treatment, batteries, supercapacitors, and sensing, is analyzed. The fundamental role of WO3 in core‐shell structures to enhance efficiency is also discussed, along with the limitations and improvement strategies. Further, the prospects of core‐shell WO3 architectures in energy conversion and environmental applications are suggested.