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The aim of this study was to investigate the possibility of predicting the concentration of β-glucan from starting barley and malt, as well as malt and wort for different types and purpose of barley groups. The strength of the correlation between types and purpose of barley groups was determined between the values of β-glucans and other indicators of cytolytic degradation. Statistically significant correlations were obtained for β-glucans in barley-malt (r = 0.9717) and barley-wort (r = 0.9998) for brewing (B w-tr) and brewing/feed winter two-row (B/Fe w-tr) varieties, and for brewing/brewing feed/feed spring varieties (B/B-Fe/Fe w-tr) between barley and Δm (Δm = β-glucan difference between barley and malt) (r = 0.8779). For the dual-purpose varieties (B/Fe w-tr), a strong correlation for β-glucans was found between malt and wort (r = 0.8188), malt and Δm* (Δm* = % of degraded β-glucan in malt in regard to the starting β-glucan in barley) (r = −0.9099), as well as Δm and Δm* (r = 0.9951). The results indicate that the starting concentration of β-glucan in barley and malt can be used as predictors of their concentration in wort only in brewing and dual-purpose (brewing-feed) varieties.