The literature reports that the consumption of common buckwheat (Fagopyrum esculentum Moench), exactly the polyphenols it contains, is associated with a wide spectrum of health benefits. Therefore, the determination of the bioaccessibility of phenolic acids and flavonoids from buckwheat biscuits formulated from liquid-state fermented flours (BBF) by selected lactic acid bacteria (LAB) after gastrointestinal digestion was addressed in this study. Bioaccessibility could be defined as the fraction of a compound that is released from the food matrix in the gastrointestinal lumen and used for intestinal absorption. The bioaccessibility of eight phenolic acids (protocatechuic, vanillic, syringic ferulic, caffeic, sinapic, p-coumaric, and t-cinnamic) and six flavonoids (epicatechin, vitexin, orientin, apigenin, kaempferol, and luteolin) were provided for BBF and BBC (buckwheat biscuits prepared from fermented and unfermented flours, respectively). The bioaccessibility indexes (BI) indicated the high bioaccessibility of phenolic acids and improved bioaccessibility of flavonoids from BBF. Moreover, the data provide evidence for the suitability of selected LAB strains to be used as natural sour agents for further bakery product development rich in phenolic acids and flavonoids with LAB-dependent bioaccessibility.