The surging climate change caused by carbon dioxide emissions primarily from the use of fossil fuels poses a threat to the global economy and civilization. Furthermore, fossil fuels are rapidly depleting, prompting the need to explore alternative and sustainable energy sources. Lignocellulosic biomass is a renewable energy source whose potential remains underexploited. Harnessing biomass energy faces challenges that limit its economic exploitation. Limited knowledge to maximize its full potential and inefficiencies experienced through the experimental stages that affect full rollout and optimal performance. An efficient valorization of lignin and cellulose components of the biomass to desired energy products remains contingent on the effective depolymerization of the biomass through pretreatment intervention. Several studies have focused on pretreatment methods such as chemical, physical, and biological separately, while few have attempted to evaluate the effect of combined methods such as physicochemical that combines physical and chemical action in biomass pretreatment. This study characterizes the lignocellulosic biomass and reviews the commonly available physicochemical pretreatment methods for improving performance in bioenergy production. The reviews examine the performance of various techniques including steam explosion, liquid hot water, ammonia fiber explosion, CO2 explosion, soaking in aqueous ammonia, and wet oxidation methods. Furthermore, the reviews focused on highlighting the performance criteria and comparing the benefits obtained from each technique.