The synthesis of fluorinated polymers via efficient routes along with mild experimental conditions is always desirable in terms of synthetic polymer chemistry. In this work, a straightforward method for fluorinated polythioether synthesis was developed. A commercially available electron-deficient alkyne compound, namely 4,4,4-trifluoro-2-butynoate (1), linked to both trifluoromethyl (CF3) and ester units was polymerized with various various dithiols by using 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as a catalyst at room temperature, yielding CF3-substituted polythioethers (CF3-polythioethers). Unlike common polymerization methods (anionic and radical) described in the literature, which include harsh conditions to produce CF3-substituted polymers, the synthetic methodology followed in this study offers mild conditions, and CF3-polythioethers with high molecular weights (M-w, up to 21.1 kDa in 1 min and up to 42.5 kDa in 1 h) were obtained in high yields in reasonably short durations. The judicious combination of polythioether chemistry with a rapid polymerization method was introduced in this study to open a way for the development of novel fluorinated polymeric materials.