Nanoscale ternary chalcogenides have attracted intense research interest due to their wealth of tunable properties and diverse applications in energy and environmental and biomedical fields. In this article, ultrasmall magnetic CuFeSe2 ternary nanocrystals (<5.0 nm) were fabricated in the presence of thiol-functionalized poly(methacrylic acid) by an environmentally friendly aqueous method under ambient conditions. The small band gap and the existence of intermediate bands lead to a broad NIR absorbance in the range of 500-1100 nm and high photothermal conversion efficiency (82%) of CuFeSe2 nanocrystals. The resultant CuFeSe2 nanocrystals show superparamagnetism and effective attenuation for X-rays. In addition, they also exhibit excellent water solubility, colloidal stability, biocompatibility, and multifunctional groups. These properties enable them to be an ideal nanotheranostic agent for multimodal imaging [e.g., photoacoustic imaging (PAI), magnetic resonance imaging (MRI), computed tomography (CT) imaging] guided photothermal therapy of cancer.