Protection of acetylenic monomers is a common practice to avoid parasitic side reactions during polymerization. Herein, we report that redox-initiated RAFT polymerization allows the direct, room temperature synthesis of a variety of single-chain nanoparticle precursors (displaying narrow molecular weight dispersity, $\overline{M}_{\rm w}$/$\overline{M}_{\rm n}$ = 1.12 1.37 up to $\overline{M}_{\rm w}$ = 100 kDa) containing well-defined amounts of naked, unprotected acetylenic functional groups available for rapid and quantitative intrachain cross-linking via metal-catalyzed carboncarbon coupling (i.e., CC click chemistry). To illustrate the useful self-clickable character of the new unprotected acetylenic precursors, single-chain nanoparticles have been prepared for the first time in a facile and highly efficient manner by copper-catalyzed alkyne homocoupling (i.e., GlaserHay coupling) at room temperature under normal air atmosphere.