Efficient and selective purify histidine (His)-rich proteins from complex biol. sample for disease initiation and progression diagnostic is crucial, but it is still a challenge. Herein, for the first time, nanomaterials composed of Prussian blue analogs (PBAs) with tailorable coordination metal ions were synthesized and operated as adsorbents for selective separation of His-rich proteins. Benefiting from the strong metal affinity forces between the His residual in protein and the immobilized Cu2+, Ni2+ and Co2+ in CuFe, NiFe and CoFe PBAs, the obtained adsorbents exhibit highly selective adsorption performance for structure-selective proteins toward bovine Hb (BHb). As a results, the maximum adsorption capacities of CuFe, NiFe and CoFe PBAs for BHb are 3365.8 mg g-1, 2421.3 mg g-1 and 1791.2 mg g-1, resp. Moreover, the high-performance CuFe, NiFe and CoFe PBAs can be easily regenerated and used to effectively separation of BHb from real bovine blood samples, permitting their excellent practicality in the complex biol. sample pretreatment, and further expanding the application scope of the traditional classical coordination compound in biochem. anal. fields.