Ion-conductive hydrogels, with ions as signal carriers, have become promising candidates to construct functional ionotronics for sensing, actuating, and robotics engineering. However, rational modulation of ionic migration to mimic biological information processing, including learning and memory, remains challenging to be realized in hydrogel materials. Here, we develop a hybrid hydrogel with optically modulated ionic conductivity to emulate the functions of a biological synapse. Through a responsive supramolecular approach, optical stimuli can trigger the release of mobile ions for tuning the conductivity of the hydrogel, which is analogous to the modulation of synaptic plasticity. As a proof of concept, this hydrogel can be used as an information processing unit to perceive different optical stimuli and regulate the grasping motion of a robotic hand, performing logical motion feedback with "learning-experience" function. Our ionic hydrogel provides a valuable strategy toward developing bioinspired ionotronic systems and pushes forward the functional applications of hydrogel materials.