<p>In this paper, we report the synthesis of two crosslinked poly(ionic liquid)s (PILs) based on 1,2,3-triazolium salt with different molecular weights of poly(ethylene oxide) (PEO) chains via photo-polymerization. Both PILs are amorphous at room temperature (RT) and thermally stable up to temperatures above 250&#xa0;°C. The glass transition temperature (T_g) of <b>2-P</b>, consisting of a longer PEO chain, is lower than that of <b>1-P</b> (shorter PEO chain) due to its lower crosslinking density. Notably, the ionic conductivity of <b>2-P</b> is higher than that of <b>1-P</b> at lower temperatures, attributed to its enhanced chain mobility. However, at higher temperatures where the kinetic limitations on polymer segmental mobility are effectively overcome, the ionic conductivity of <b>1-P</b> eventually catches up with that of <b>2-P</b>. This indicates that the conductivity at elevated temperatures is governed primarily by charge carrier density rather than chain mobility restrictions. Consequently, the ionic conduction behavior of the PILs based on triazolium salt can be modulated by the PEO chain length; specifically, <b>2-P</b> demonstrates superior ionic conduction at RT, while <b>1-P</b> exhibits high conduction efficiency at elevated temperatures owing to its high charge density.</p> Graphic abstract <p></p>