Two novel exopolysaccharides, named LPB8-0 and LPB8-1, were isolated and purified from Lactiplantibacillus pentosus B8. Moreover, their structure and bioactivities were evaluated through chemical and spectral means. The study results demonstrated that LPB8-0 was primarily composed of mannose and glucose and had an average molecular weight of 1.12 × 104 Da, while LPB8-1 was composed of mannose, glucose, and galactose and had an average molecular weight of 1.78 × 105 Da. Their carbohydrate contents were 96.2% ± 1.0% and 99.1% ± 0.5%, respectively. The backbone of LPB8-1 was composed of (1→2)-linked α-D-Manp and (1→6)-linked α-D-Manp. LPB8-0 and LPB8-1 had semicrystalline structures with good thermal stability (308.3 and 311.7 °C, respectively). SEM results displayed that both LPB8-0 and LPB8-1 had irregular thin-slice shapes and spherical body structures. Additionally, an emulsifying ability assay confirmed that LPB8-0 and LPB8-1 had good emulsifying activity against several edible oils, and this activity was retained under acidic, neutral, and high temperature conditions. Furthermore, an antioxidant assay confirmed that LPB8-1 had stronger scavenging activity than LPB8-0. Overall, these results provide a theoretical basis for the potential application of these two novel exopolysaccharides as natural antioxidants and emulsifiers in the food and pharmaceutical industries.