The paper presents the comparative qualitative and quantitative analysis of twelve algorithms for training artificial neural networks (ANN) which predict the higher heating value (HHV) of biomass based on the proximate analysis (fixed carbon, volatile matter, and ash percentage). The twelve networks, with the same structure but different training algorithm, were fed with 318 experimental data triplets from literature for different biomass species and trained with 318 corresponding HHV values used for the supervised learning. Our comparative analysis showed that several algorithms resulted in ANNs generating outputs well correlated with the true measured values of the biomass HHV. Of those, Levenberg-Marquardt algorithm gives the best results in terms of mean squared error calculated on the training set data, while Bayesian regularization gives the best results in terms of regression. When applied to new datasets, unknown to the ANNs trained here, the highest accuracy of the HHV prediction was obtained by Conjugate Gradient, Powell/Beale Restarts training function. It ensured prediction based on the unknown datasets better than Levenberg-Marquardt algorithm. The described approach can be used for predicting the calorific values of different biomass species, including newly proposed ones, as well as for optimizing the HHV for both pure biomass and biomass mixtures.