Lactiplantibacillus pentosus is a lactic acid bacterium frequently detected in various fermented foods; however, the genomic traits related to its biotechnological potential have been underexplored. In this study, 34 catalase-negative isolates were obtained from pickled mustard greens, among which strain P7 exhibited the highest exopolysaccharide (EPS) yield (781.9 ± 14.7 mg/L) and was capable of growing in a chemically defined medium lacking riboflavin. Whole-genome sequencing revealed a 3,749,478 bp circular chromosome with 46.5% G + C content and 3389 protein-coding genes. A phylogenomic analysis identified P7 as L. pentosus. Functionally, 1 mg/mL EPS extracted from P7 demonstrated strong antioxidant activity, with DPPH and hydroxyl radical scavenging capacities of 89.8 ± 4.6% and 76.5 ± 9.5%, respectively. The use of 0.2 mg/mL EPS also protected Saccharomyces cerevisiae cells from oxidative stress. A comparative genomic analysis indicated the presence of nearly complete biosynthetic pathways for riboflavin, folate, and pyridoxine. High-performance liquid chromatography (HPLC) confirmed the production of 23.8 ± 0.4 µg/mL riboflavin, 36.6 ± 0.6 µg/mL folic acid, and 0.42 ± 0.02 µg/mL pyridoxine in the culture supernatant, which have not been previously reported. Additionally, strain P7 produced 91.2 ± 12.3 g/L of lactic acid after 24 h of incubation. These results support the potential of L. pentosus P7 as a candidate for industrial applications in the production of EPS, B-group vitamins, and lactic acid.