Selenium-containing polymers are a group of fascinating functional polymers with unique structures, properties, and applications, which have been developed recently but only with limited examples. The challenges of developing selenium-containing polymers with structural and functional diversity include the lack of economic and safe monomers, lack of efficient and convenient synthetic approaches, and poor stability of selenium-involving covalent bonds. In this work, room-temperature metal-free multicomponent polymerizations (MCPs) of elemental selenium, diisocyanides, and dipropargyl alcohols were developed, and polymers with a selenium-containing aliphatic heterocycle, 1,3-oxaselenolane, were synthesized through these MCPs directly from elemental selenium. The alicyclic poly(oxaselenolane)s enjoyed high yields (up to 93%), high molecular weights (up to 15 600 g/mol), high thermal and chemical stability, good solubility and processability. With the structural design of the poly(oxaselenolane)s and their high selenium contents of up to 33.7 wt %, the refractive indices of their spin-coated thin films could reach 1.8026 at 633 nm and maintain 1.7770 at 1700 nm. It is anticipated that these efficient, convenient, mild, and economic multicomponent polymerizations of elemental selenium can promote the selenium-related polymer chemistry and accelerate the exploration of diversified selenium-containing functional polymer materials.