The synthesis of nanostructures using homogeneous precursors in the solution phase is widely used to achieve uniformity and well‐defined morphological control. However, drawbacks such as the lack of diversity due to the limited reaction rate modulation exist. One‐step, core–shell nanorod formation using simultaneous covering synthesis using solid and ionic heterogeneous precursors is proposed in this study. A Te‐Bi2Te3/TeO2 core–shell structure is successfully synthesized by precisely controlling various influencing factors, including concentration, temperature, and pH, and its physicochemical and photochemical properties are thoroughly investigated. The proposed nanostructure overcomes the oxidation susceptibility of Te and can be applied to multipotent cancer theranostics in vitro and in vivo in combination with computed tomography imaging.