The energy efficiency of capacitive deionization (CDI) with porous carbon electrodes is limited by the high ionic resistance of the macropores in the electrodes. In this study, we demonstrate a facile approach to improve the energy efficiency by filling the macropores with ion-conductive polyelectrolytes, which is termed polyelectrolyte-infiltrated CDI (pie-CDI or πCDI). In πCDI, the filled polyelectrolyte effectively turns the macropores into a charged ion-selective layer and thus increases the conductivity of macropores. We show experimentally that πCDI can save up to half of the energy consumption compared to membrane CDI, achieving identical desalination during the charging step. The energy consumption can be even lower if the process is operated at a smaller average salt adsorption rate. Further energy breakdown analysis based on a theoretical model confirms that the improved energy efficiency is largely attributed to the increased conductivity in the macropores.