In clinical treatment of cancer diseases a significant and constantly increasing role play platinum coordination compounds. Among them, cisplatin and its analogues take unquestionably leading position due to their specific cytotoxic action against certain kinds of malignancies. The fundamental challenge created by the needs of the contemporary chemotherapy is development of new generation drugs, possessing a wider spectrum of action and a lesser toxicity. Biological activity of newly designed and established metallodrugs can be estimated, among other functions, by the characterization of their interactions with plasma transport proteins, e.g., albumin and transferrin. For such investigations, various techniques have been applied, but the necessity for off-line separation of the components of the reaction mixture made the existing analytical methodology rather time-consuming and inefficient. Therefore, techniques with a higher separation ability and minor impact on the original species distribution become of major concern. One of these is capillary electrophoresis (CE) that being hyphenated with inductively coupled plasma (ICP-MS) or electrospray ionization mass spectrometric detection offers great potential in metallodrug investigation. Hyphenated CE-ICP-MS technique is proposed for the identification and characterization of free and protein-bound fractions in systems comprising various platinum group metal complexes and human serum proteins.