This study aims to identify an equation for predicting the calorific value for heat-treated biomass using structural analysis. Different models were constructed using 129 samples of cellulose, hemicellulose, and lignin, and calorific values obtained from previous studies. These models were validated using 41 additional datasets, and an optimal model was identified using its results and following performance metrics: the coefficient of determination (R2), mean absolute error (MAE), root-mean-squared error (RMSE), average absolute error (AAE), and average bias error (ABE). Finally, the model was verified using 25 additional data points. For the overall dataset, R2 was ~0.52, and the RMSE range was 1.46–1.77. For woody biomass, the R2 range was 0.78–0.83, and the RMSE range was 0.9626–1.2810. For herbaceous biomass, the R2 range was 0.5251–0.6001, and the RMSE range was 1.1822–1.3957. The validation results showed similar or slightly poorer performances. The optimal model was then tested using the test data. For overall biomass and woody biomass, the performance metrics of the obtained model were superior to those in previous studies, whereas for herbaceous biomass, lower performance metrics were observed. The identified model demonstrated equal or superior performance compared to linear models. Further improvements are required based on a wider range of structural biomass data.