Freeze-thaw is a common stress at high altitudes in northern China. There is a risk of cadmium (Cd) contamination in the region. γ-aminobutyric acid (GABA) is a natural product that regulates plant growth. Rye (Secale cereale ) was used as research material to investigate the physiological effects of exogenous GABA on rye seedlings under the single and combined stresses of freeze-thaw and cadmium. The results showed that the combined stress severely inhibited shoot length, root length, fresh weight, and dry weight, increased malondialdehyde and hydrogen peroxide contents, and significantly decreased superoxide dismutase (SOD) activity. Foliar application of 5mM GABA alleviated the negative effects of stress on seedling growth, increased soluble protein content, and reduced malondialdehyde and hydrogen peroxide contents. Exogenous GABA application also enhanced the activities of SOD and peroxidase (POD). Additionally, the presence of exogenous GABA activated the GABA metabolic process and encouraged the accumulation of phytochelatins, glutathione, and non-protein thiol. These results indicate that exogenous GABA can effectively improve the resistance of rye seedlings to freeze-thaw and Cd by regulating the antioxidant enzyme system and enhancing its own detoxification mechanism, and they provide a basis for future applications of exogenous GABA, which is beneficial for ecological protection.