SummaryFourteen hull‐less barley cultivars, collected from four major cultivated areas in China, were employed to investigate the structural and physicochemical properties of their starches in this study. Relatively wide variations in physicochemical properties of the starches were observed. Amylose content ranged from 23.1% to 30.0%, swelling power and water solubility index ranged from 12.8 to 19.9 g g−1 and 12.7% to 23.7% respectively. Peak viscosity was from 170 to 346 Rapid Visco Unit (RVU), peak temperature (Tp) of starch gelatinisation was from 55.6 to 61.8 °C and enthalpy of starch retrogradation ranged from 0.3 to 3.1 J g−1. Weight‐based chain‐length proportions of fa, fb1, fb2 and fb3 in amylopectins ranged from 21.65% to 24.95%, 44.48% to 49.44%, 15.56% to 17.19% and 9.83% to 16.66% respectively. Correlation analyses showed that amylose content was inversely related to pasting parameters and enthalpy of gelatinisation. Pasting properties and amylopectin structures were the most important parameters to differentiate starch properties among different hull‐less barley cultivars in this study. This work will be useful for exploring applications of Chinese hull‐less barley starches in food and non‐food industries.