Ten different barley varieties grown in one location were studied for their content of tocols, folate, plant sterols, alkylresorcinols, and phenolic acids, as well as dietary fiber components (arabinoxylan and beta-glucan). The samples included hulled and hull-less barley types and types with normal, high-amylose, and waxy starch. The aim was to study the composition of raw materials, and therefore the hulls were not removed from the hulled barleys. A large variation was observed in the contents of all phytochemicals and dietary fibers. Two varieties from the INRA Clermont Ferrand barley program in France (CFL93-149 and CFL98-398) had high content of tocopherols and alkylresorcinols, whereas the variety Dicktoo was highest in dietary fiber content and phenolics. Positive correlations were found between 1000 kernel weight, alkylresorcinols, and tocols, as well as between dietary fiber content and phenolic compounds. The results demonstrate that the levels of phytochemicals in barley can likely be affected by breeding and that the contents of single phytochemicals may easily be adjusted by a right selection of a genotype.