Perennial grasses display several positive attributes as suitable energy crops for use as a solid fuel for direct combustion, such as high annual production of dry matter per unit area, perennity and high harvest flexibility. This study aimed to characterize the chemical composition and calorific value of 18 elephant grass (EG) varieties (Pennisetum purpureum Schum.) and 10 other potential bioenergy feedstocks intended for direct combustion. Samples were obtained from 6‐month‐old EG and sorghum and 3‐year‐old eucalyptus, Mimosa caesalpiniaefolia, and bamboo plants. Sugarcane bagasse and straw, rice husk, corn stover, coconut husk, and fiber samples were also evaluated. The elemental composition, lower heating value (LHV), and cellulose (CEL), hemicellulose (HCEL), lignin (LIG) and ash contents (% dry matter) were analyzed. The results indicated that the EG genotypes showed significant differences when compared with other evaluated biomasses, but showed no differences among themselves. The EG varieties showed a mean LHV (16.7 MJ/kg) superior to that of rice husk, sugarcane bagasse, and sorghum and similar to that of sugarcane straw, coconut fiber, and corn stover. The EG varieties showed a mean ash content (4.74%) inferior to that of rice husk, sugarcane bagasse, coconut fiber, and sorghum; a mean CEL content (36.0%) similar to that of sugarcane straw, coconut fiber, corn stover, sorghum, and Mimosa caesalpinifolia; HCEL; a mean HCEL content (30.3%) superior to that of rice husk, bamboo, eucalyptus, M. caesalpinifolia, coconut husk, and fiber; and a mean LIG content (8.80%) superior to that of corn stover and similar to that of sorghum, sugarcane bagasse, and straw biomass. The significant capacity of EG to accumulate dry matter was associated with the biomass quality attributes (LHV and CEL, HCEL, LIG, and ash contents), thereby making it an excellent alternative to lignocellulosic feedstock for direct combustion.