The article justifies the expediency of the breeding of barley cultivars with waxy starch, grain of which can be raw material for functional food production. The study purpose was to create food barley cultivars with waxy starch. To accomplish this, qualitative parameters of barley accessions were determined, and starting material was selected for breeding. The study was conducted at the Plant Production Institute named after V.Ya. Yuriev of NAAS in 2015–2017. Twenty four chaffy and naked barley accessions of different origin were taken as the test material. Grain quality parameters of wild type and waxy accessions were compared. The yield, protein and starch contents, endosperm vitreousness, and antioxidant activity were shown to depend both on growing conditions and on genotypes. High nutritional quality of waxy barley cultivars was proved, videlicet, significantly higher content of oil compared with accessions with wild type starch and lower vitreousness of endosperm in chaffy accessions. Accessions with very valuable characteristics were selected: line 12-1014 with high digestibility of protein (61.75 mg tyrosine/g protein for pepsinolysis + trypsinolysis), line 12-945 with high antioxidant activity (2.02 mg chlorogenic acid equivalent/g), line 12-954 with a high content of oil (3.75%) and awnless line 14-1183 with a high content of polyunsaturated ω-3 linolenic acid (6.09%). These lines are valuable both as starting material for the breeding of food cultivars, and directly for functional food production. Waxy cultivars Shedevr and Amil were submitted to the state variety trials. Grain of these cultivars is noticeable for high contents of starch (>60%), oil (3.45–3.47%) and fiber (3.65–3.70%). Antioxidant activity is also sufficiently high (1.94–2.07 mg chlorogenic acid equivalent/g). Being low vitreous (40–43%), cultivars Shedevr and Amil can be used for production of flakes and flour, including extruded flour.