Abstract <p>The effect of top-dressing at tillage phase by Polydon® Amino Start organo-mineral fertilizer and KAS-28 liquid mineral fertilizer on the state of the leaf pigment complex of spring barley cv. Novichok, Rodnik Prikamya, and Pamyati Rodinoy and their relationship with grain quality parameters were studied under field conditions of Kirov oblast of the Russian Federation in 2020–2022. The significant effect of top-dress treatments on pigment content in the flag and second leaves was revealed. The use of top-dressing with KAS-28 enhanced the association of grain quality parameters with the chlorophyll pigment content of the two upper leaves compared to the control variant. The effect of Amino Start was not uniform: some of the correlations were somewhat weakened compared to the control, some intensified, and some became statistically significant. The total content of chlorophyll correlated with the content of cellulose and fat in the grain in all treatments. Compared to controls, the use of top-dress treatments altered the effectiveness of the use of photoassimilates of both leaves for cellulose and fat synthesis. The data obtained indicate the possibility of predicting the content of the main parameters of spring barley’s grain quality by the content of chlorophyll pigments in the flag or second leaves of plants during the flowering phase.</p>