The glass transition induces substantial changes in material properties, transforming a stiff glass into a soft rubber. Like other polymeric materials, polyelectrolyte complex (PEC) undergoes a glass transition at elevated temperature and with the presence of salt. Here, we demonstrated electrical modulation of Tg of the PECs in tri-layer structure, sandwiched by two oppositely charged ionoelastomers (IEs). Under external electric potential, the IEs can inject and extract their counter-ions from the PECs, inducing glass-transition governed by time-temperature-salt superposition (TTSS) principle. This real-time, reversible glass transition produces large, reversible changes in ion conductivity, enabling kinetically driven ionic diodes.