Phototheranostic based on photothermal therapy (PTT) and photoacoustic imaging (PAI), as one of avant-garde medical techniques, have sparked growing attention because it allows noninvasive, deeply penetrative, and highly selective and effective therapy. Among a variety of phototheranostic nanoagents, single-component inorganic nanostructures are found to be novel and attractive PAI and PTT combined nanotheranostic agents and received tremendous attention, which not only exhibit structural controllability, high tunability in physiochemical properties, size-dependent optical properties, high reproducibility, simple composition, easy functionalization, and simple synthesis process, but also can be endowed with multiple therapeutic and imaging functions, realizing the superior therapy result along with bringing less foreign materials into body, reducing systemic side effects and improving the bioavailability. In this review, according to their synthetic components, conventional single-component inorganic nanostructures are divided into metallic nanostructures, metal dichalcogenides, metal oxides, carbon based nanostructures, upconversion nanoparticles (UCNPs), metal organic frameworks (MOFs), MXenes, graphdiyne and other nanostructures. On the basis of this category, their detailed applications in PAI guide PTT of tumor treatment are systematically reviewed, including synthesis strategies, corresponding performances, and cancer diagnosis and therapeutic efficacy. Before these, the factors to influence on photothermal effect and the principle of in vivo PAI are briefly presented. Finally, we also comprehensively and thoroughly discussed the limitation, potential barriers, future perspectives for research and clinical translation of this single-component inorganic nanoagent in biomedical therapeutics.