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The present investigation is vital for logistic and costs improvement of lignocellulosic biomass for energy production. In this study, radio-frequency (RF)-based dielectric heating technique was used in the alkaline (NaOH) pretreatment of lignocellulosic biomass (barley straw), so as to enhance the breakdown and accessibility of the cross-linking binding lignin. Three levels of temperature (70C, 80C, and 90C), five levels of ratio of biomass to NaOH solution (1:4, 1:5, 1:6, 1:7, & 1:8), 1 h equilibration time, screen size of 1.6 mm, 1% NaOH concentration, and 20 min residence time were used for the radio frequency pretreatment. The effect of radio frequency pretreatment was assessed through densification of the pretreated and non-pretreated biomass samples. It was observed that the use of NaOH solution and the ratio of biomass to NaOH solution played a major role in the breakdown of the lignified matrix, as well as in the production of pellets with good quality physical characteristics. However, the use of NaOH increased the ash content of the biomass. Washing of the pretreated sample with tap water decreased the ash content, but reduced the quality of the produced pellets.