Secondary metabolites in potato tubers include both phytonutrients and plant defense compounds. The extent these small molecules vary among different potato genotypes is not well characterized. LC-MS analysis of tuber extracts from seven potato genotypes showed that one large source of small molecule variation is the glycoalkaloids. Glycoalkaloids are involved in the resistance of potatoes to pathogens and pests, but they also have implications for human health and nutrition. This study focused on glycoalkaloids with solanidane or solanidane-like aglycones, of which over 50 were tentatively identified, many of which appeared to be novel glycoalkaloids. Results suggested the variety of glycoalkaloids in potatoes is considerably greater than previously thought. Dissecting the role of these many glycoalkaloids in human health or pest and pathogen resistance will be a formidable undertaking.