Primulina plants native to karst regions are exceptionally rich in calcium and have been developed into high‑calcium leafy vegetables. However, limited knowledge of their metabolites, taste characteristics, and potential medicinal value restricts further genetic improvements. This study conducted a comprehensive analysis on three breeding species of Primulina vegetables. Common garden experiment demonstrated significant calcium enrichment capability, with calcium content ranging from 204.45 to 391.52 mg/100 g. Through widely-targeted metabolomics, 1121 metabolites were identified within these Primulina vegetables. Furthermore, comparative analysis identified 976 differentially accumulated metabolites across nine comparison groups, driven mainly by flavonoids, phenolic acids, and lipids. Integration of electronic tongue analysis and metabolomics revealed taste profiles and identified 17 key candidate compounds related to taste. Based on network pharmacology analysis, 32 active ingredients were found in Primulina vegetables, which highlighted potential medicinal value. These findings provide a data-driven foundation for breeding programs aimed at enhancing nutritional and flavor traits.