We report the deterrent, toxic, and antireproductive effect of several Solanum glycoalkaloids on the potato aphid, Macrosiphum euphorbiae, and discuss the structure–activity relationship of the tested compounds. The results indicate a structure-dependent biological effect of the glycoalkaloids, suggesting that, while the structure of the aglycone defines a basal biological effect, the carbohydrate moiety is crucial for the overall biological effect.