Photoacoustic (PA) imaging is a burgeoning imaging modality that has a broad range of applications in the early diagnosis of cancer, detection of various diseases, and relevant scientific research. It is a non-invasive imaging modality that relies on the absorption coefficient of the imaging tissue and the injected PA-imaging contrast agent. Nevertheless, PA imaging exhibits weak imaging depth due to its exponentially decaying signal intensity with increasing tissue depth. To improve the depth and heighten the contrast of imaging, a series of PA contrast agents has been developed based on nanomaterials. In this review, we present a comprehensive overview of recent advancements in contrast agents for photoacoustic (PA) imaging, encompassing the emergence of first near-infrared region (NIR-I, 700-950 nm) PA contrast agents, second near-infrared region (NIR-II, 1000-1700 nm) PA contrast agents, and ratiometric PA contrast agents. Subsequently, the latest advances in PA image-guided cancer therapy were introduced, such as photothermal therapy (PTT), photodynamic therapy (PDT), sonodynamic therapy (SDT), and PTT-based synergistic therapy. Finally, the prospects of PA contrast agents and their biomedical applications were also discussed. This review provides a systematic summary of the development and utilization of the cutting-edge photoacoustic agents, which may inspire fresh thinking in the fabrication and application aspects of imaging agents.