Technical Abstract: Sunn hemp (Crotolaria juncea), is a fast growing, high biomass yielding tropical legume that may be a possible southeastern bioenergy crop. When comparing this legume to a commonly grown summer legume—cowpeas (Vigna unguiculata), sunn hemp was superior in biomass yield and subsequent energy yield. Sunn hemp had 10.7 Megagrams per hectare of biomass with an energy content of 19.0 Megajoules per kilogram after 12 weeks of growth in one year of the study. This resulted in an energy yield of 204 Gigajoules per hectare. The energy content was 6% greater than that of cowpeas. Even though sunn hemp had a greater amount of ash, plant nutrient concentrations were lower in some cases of minerals (K, Ca, Mg, S) known to reduce thermochemical conversion process efficiency. Pyrolytic degradation of both legumes revealed that sunn hemp began to degrade at higher temperatures as well as release greater amounts of volatile matter.