Grasses have sufficient potential to be used in the biofuel industry due to many reasons. Hence, systematic assessments of the lignocellulosic biomass obtained from six grasses namely Arundo donax, Chrysopogon zizanioides, Coix lacryma-jobi, Pennisetum purpureum, Saccharum spontaneum, and Sorghum bicolor have been performed to assess their potential for bioethanol production. Selected morphological (height, internode diameter, number of internodes, fresh biomass, dry biomass, total volatile matter), anatomical (vascular bundle, stain intensity), analytical (crystallinity index of cellulose, thermal stability, hemicellulose, moisture content) and biochemical (α-cellulose, acid insoluble lignin) parameters were investigated and statistically analysed to detect the superior grass species. The study indicates that S. spontaneum harbours promising biofuel potential by having high dry biomass (56.33 g), α-cellulose (55.88–67.76%), but lower thermal stability (Tmax: 344.37 °C). Comparable ligno-cellulose properties with respect to dry biomass (54.60 g), α-cellulose content (45.95–64.14%), Tmax (360.51 °C) have been observed for A. donax. However, relatively higher lignin contents (∼17–23%) and crystalline cellulose (43.63%–46.96%) in S. spontaneum and A. donax might have resulted into lesser saccharification yield (216.04–230.08 mg/g). On that aspect, S. bicolor and C. lacryma-jobi might be useful since they possessed lower lignin (14.03–16.56%) and crystalline cellulose (32.51–33.02%) leading to higher glucose yield (263–420.06 mg/g). Taken together, this study indicates that integration of morphological, biochemical, and analytical properties of biomasses are complex, yet useful to predict a ‘superior donor plant’ for bioenergy purposes.