Polyelectrolyte gels are an important class of polymer gels and a versatile platform with charged polymer networks with ionisable groups. They have drawn significant recent attention as a class of smart material and have demonstrated potential for a variety of applications. This review begins with the fundamentals of polyelectrolyte gels, which encompass various classifications (i.e., origin, charge, shape) and crucial aspects (ionic conductivity and stimuli responsiveness). It further centralises recent developments of polyelectrolyte gels, emphasising their synthesis, structure–property relationships and responsive properties. Sequentially, this review demonstrates how polyelectrolyte gels’ flourishing properties create attractiveness to a range of applications including tissue engineering, drug delivery, actuators and bioelectronics. Finally, the review outlines the indisputable appeal, further improvements and emerging trends in polyelectrolyte gels.