Multicomponent polymerizations (MCPs) have emerged as a powerful tool in the synthesis of advanced, sequence-regulated polymers based on their mild reaction conditions, ease of use, and high atom economy. Herein, we exploit MCP methodology to introduce elemental selenium into a polymer chain, accessing a unique polymer class,i.e., polyselenoureas. These polyselenoureas can be synthesized from a broad range of commercially available starting materials, in a simple ambient temperature one-step procedure. The incorporation of selenium directly into the polymer backbone provides a unique handle for polymer characterization based on the distinctive isotope profiles exposed by high-resolution mass spectrometry, along with diagnostic signals observed in infrared and X-ray photoelectron spectroscopies. In addition, diffusion ordered spectroscopy provides access to hydrodynamic diameter information on the generated unique polymer class.