Rhodiola species are renowned medicinal plants with centuries of traditional use and broad pharmacological effects. In recent years, market and economic factors have fueled widespread adulteration in the global Rhodiola product market. More critically, much potential adulteration may remain undetected, since authenticating the species of raw materials in processed products is particularly challenging: morphological, microscopic, and genetic methods are often invalidated by manufacturing processes. In contrast, phytochemical constituents remain traceable from raw materials to finished products, offering a promising avenue for authentication. Regrettably, the lack of reliable chemical markers for Rhodiola species identification hinders effective adulteration detection and market supervision. This paper aims to comprehensively review phytochemical constituents from the genus Rhodiola as the critical first step toward marker discovery. Multiple academic databases were searched to summarize chemical names, molecular formulas, structures, and botanical sources of documented compounds. The genus exhibits remarkable chemical diversity, with over 500 compounds classified into eight groups: phenylalkanoid derivatives, phenylpropanoids, flavonoids, terpenoids, phenolics and organic acids, cyanogenic glycosides, steroids, and others. Further analysis qualitatively delineates both interspecific chemical similarities (most compounds are shared across species) and differences (distinct combinations of shared compounds and compounds currently known from single species). These findings collectively elucidate the inherent challenges and potential feasibility of discovering chemical markers for Rhodiola species identification. Meanwhile, the consolidated phytochemical data serves as a foundational compound database, ensuring higher accuracy and reliability in subsequent UPLC-MS-based compound identification. Additionally, to reduce analytical complexity in marker exploration, this paper advocates shifting the focus from solely species-specific compounds to broader chemical characteristics (encompassing species-specific compounds, content levels, and content ratios), and proposes a hierarchical “chemical characteristics + classification tree” framework for stepwise identification. Finally, we outline a research plan to implement these strategies, comprising the completed phytochemistry review, sample collection, UPLC-MS-based qualitative profiling, UPLC-based quantitative analysis, and multivariate data analysis. In conclusion, this paper highlights the importance of developing a reliable chemical identification method for Rhodiola species, provides an essential chemical foundation and strategic guidance for future marker discovery, and ultimately aims to solve raw material authentication in Rhodiola preparations to combat adulteration and strengthen market supervision.