Alfalfa stems, reed canarygrass, and switchgrass; perennial herbaceous species that have potential as biomass energy crops in temperate regions; were evaluated for their bioconversion potential as energy crops. Each forage species was harvested at two or three maturity stages and analyzed for carbohydrates, lignin, protein, lipid, organic acids, and mineral composition. The biomass samples were also evaluated for sugar yields following pretreatment with dilute sulfuric followed by enzymatic saccharification using a commercial cellulase preparation. Total carbohydrate content of the plants varied from 518 to 655g kg(-1) dry matter (DM) and cellulose concentration from 209 to 322g kg(-1) DM. Carbohydrate and lignin contents were lower for samples from early maturity samples compared to samples from late maturity harvests. Several important trends were observed in regards to the efficiency of sugar recovery following treatments with dilute acid and cellulase. First, a significant amount of the available carbohydrates were in the form of soluble sugars and storage carbohydrates (4.3-16.3% wt/wt). Recovery of soluble sugars following dilute acid pretreatment was problematic, especially that of fructose. Fructose was found to be extremely labile to the dilute acid pretreatments. Second, the efficiency at which available glucose was recovered was inversely correlated to maturity and lignin content. However, total glucose yields were higher for the later maturities because of higher cellulose contents compared to the earlier maturity samples. Finally, cell wall polysaccharides, as determined by the widely applied detergent fiber system were found to be inaccurate. The detergent fiber method consistently overestimated cellulose and hemicellulose and underestimated lignin by substantial amounts. Published by Elsevier Ltd.