A heuristic methodology to estimate higher heating values (HHV) based on a statistic tools, in particular, hierarchical cluster analysis, is disclosed in this paper. The correlation has been studied using data available in other documents, and as test samples were used biomasses from open sources or also from previously published works. The aim is to offer another fast and simple way to access the information regarding the higher heating value. The method was tuned for lignocellulosic biomass and have presented an average absolute error lower than 3% and marginal average bias error at just -0.52% indicating a good predictive capability.