Biodegradable artificial synapses hold great promise for sustainable neuromorphic electronics, yet combining long-term memory, ultralow energy consumption, and mechanical robustness remains challenging. Here, we report a fully biodegradable multilayer artificial synapse (M-AS) composed of crosslinked chitosan-guar gum (CS-GG) ion-active layers (IALs) and a cellulose acetate (CA) ion-binding layer (IBL). This trilayer architecture enhances ion trapping via ion-dipole coupling (IDC) at the IAL-IBL interface, while hydrogen-bonded crosslinking within the CS-GG matrix enhances mechanical and environmental stability. Sodium chloride, embedded in the IALs, serves as a mobile ionic species analogous to biological neurotransmitters, enabling low-voltage ion migration. Upon electrical stimulation, ion migration and dipole alignment induce IDC, leading to partial ion retention and cascade-like postsynaptic current responses that support memory formation. The M-AS supports key synaptic functionalities-including paired-pulse facilitation, short-term and long-term plasticity, multilevel memory encoding, and bidirectional modulation-under sub-millivolt operation. It achieves the longest long-term memory time (5944 s) reported among biodegradable artificial synapses and an energy consumption (0.85 fJ/event) lower than that of biological synapses. Integration with a thermistor and robotic actuator enables a bioinspired reflexive system capable of adaptive, stimulus-dependent learning and reflex-like behaviors. These results demonstrate the potential of M-AS for low-power, intelligent human-machine interfaces.