The controlled folding of a single polymer chain is for the first time realized by metal‐ complexation. α,ω‐Bromine functional linear polymers are prepared via activators regenerated by electron transfer (ARGET) ATRP (,SEC = 5900 g mol?1, ? = 1.07 and 12 000 g mol?1, ? = 1.06) and the end groups of the polymers are subsequently converted to azide functionalities. A copper‐catalyzed azide–alkyne cycloaddition (CuAAC) reaction is carried out in the presence of a novel triphenylphosphine ligand and the polymers to afford homotelechelic bis‐triphenylphosphine polymeric‐macroligands (MLs) (,SEC = 6600 g mol?1, ? = 1.07, and 12 800 g mol?1, ? = 1.06). Single‐chain metal complexes (SCMCs) are formed in the presence of Pd(II) ions in highly diluted solution at ambient temperature. The results derived via 1H and 31P{1H} NMR experiments, SEC, and DLS unambiguously evidence the efficient formation of SCMCs via metal ligand complexation.