Phytosterols are plant sterols that present several benefits for human health. In crop species, such as sunflower, oil phytosterol concentration shows genetic and environmental variations. The reasons that cause such varied concentration of phytosterols in the oil are unknown. The aim of this work was to investigate the relationships between phytosterol concentration and composition and grain oil content in sunflower. Two sets of samples, with lines and hybrids grown in different environments in Argentina and Spain, were used to establish and validate the relationships between phytosterols and grain oil content. Oil phytosterol concentration decreased in both types of genotypes, lines, and hybrids, when oil content per grain increased. A dilution-like relationship accounted for 82% of the variability in phytosterol concentration among genotypes and environments. Phytosterol concentration rapidly increased with oil contents lower than 11.4 mg per grain. This relationship was observed for total phytosterols and each type of the phytosterols analyzed. With low oil per grain, phytosterol composition varied, with higher proportions of β-sitosterol and Δ 7 -stigmastenol. The relationships established in this work could serve to design breeding and crop management strategies.