Intelligent applications, with tactile sensors at their core, represent significant advancement in the field of artificial intelligence. However, achieving perception abilities in tactile sensors that match or exceed human skin remains a formidable challenge. Consequently, the design and implementation of hierarchical structural materials are considered the optimal solution to this challenge. In contrast to conventional methods, such as complicated lithography and three‐dimensional printing, the cost‐effective and scalable nature of advanced solution‐synthesis methods makes them ideal for preparing diverse tactile sensors with hierarchical structural materials. However, the process and applicability of advanced solution synthesis methods have yet to form a seamless system. Accordingly, the development and intellectualization of tactile sensors based on advanced solution synthesis methods are still in their early stages, and require a comprehensive and systematic review to usher in progress. This study delves into the advantages and disadvantages of various advanced solution synthesis methods, providing detailed insights. Furthermore, the positive effects of hierarchical structural materials constructed using these methods in tactile sensors and their intelligent applications are also discussed in depth. Finally, the challenges and future opportunities faced by this emerging field are summarized.image