In this study, changes of bioactive compounds (crude protein (CP), crude fat (CF), dietary fiber (DF), fatty acids (FAs), free amino acids (FAAs), phenolic compounds (PCs), biogenic amines (BAs), lignans, and alkylresorcinols) in barley industry by‐products (BB) during submerged and solid state fermentation (SSF) with Pediococcus acidilactici were analyzed. It was established that both fermentation conditions reduce the CP and CF content in BB (by 25.8% and 35.9%, respectively) and increase DF content (on average by 25.0%). Fermentation increases the oleic, arachidic, eicosadienoic, behenic, and lignoceric FA in BB samples. The highest total BA content was found in untreated samples (290.6 mg/kg). Solid state fermentation increased the content of the alkylresorcinol C19:0. Finally, collecting data about the changes of these compounds during technological processes is very important, because according to the specific compounds formed during fermentation, further recommendations for by‐product valorization and uses in food, pharmaceutical, or feed industries can be suggested. The submerged and solid state fermentation with Pediococcus acidilactici change bioactive compounds content in barley industry by‐products. The changes of bioactive compounds during technological processes are very important, because the specific and useful compounds formed during fermentation. Fermented by‐product can be suggested for valorization and uses in food, pharmaceutical, or feed industries.