The objective of this work was to determine the potential of germplasm from the Germplasm Enhancement of Maize (GEM) programme for use as a biofuel feedstock, relative to commercial grain and silage hybrids. Eighteen maize genotypes including GEM varieties and commercial checks were evaluated in a 2-year field study for dry matter yield, moisture at harvest and sugar produced by hydrolysis of whole plants and cobs. There were no significant correlations between any of the traits measured, suggesting that it should be possible to improve yield with quality traits using a selection index. A brown midrib variety was in the top significance group for hydrolysis traits, underscoring the impact of this mutation on the digestibility of lignocellulosic biomass. Commercial varieties tended to have superior dry matter yield, while several GEM lines ranked highly for sugar produced by hydrolysis of whole plants. Selection indices that take both sugar produced by hydrolysis and dry matter yield into account produced rankings of the germplasm used in this study that were markedly different than rankings based on either trait alone.