Biologically active natural folate form L-5-methyltetrahydrofolate is less stable than synthetic folate form folic acid commonly used for food fortification. The production of electrosprayed capsules using a combination of carbohydrates such as glucose syrup and pullulan was investigated to provide higher stability of L-5-methyltetrahydrofolate in food products. Additionally, the protective effect of ascorbic acid, if added to the biopolymer solution for capsules production was investigated. During the production of electrosprayed capsules containing L-5-methyltetrahydrofolate, both with and without ascorbic acid, the recovery of folate was >97%. During storage at 22 °C for 21 days, the electrosprayed capsules (with or without ascorbic acid) showed significantly higher folate recovery compared to free L-5-methyltetrahydrofolate (91% vs. 61%, p ≤ 0.05). In buns baked with all-purpose flour fortified with the free form or the electrosprayed capsules, which were stored at 22 °C for 9 days, no significant difference was shown for the retention of the L-5-methyltetrahydrofolate.