The pellet energy market is expanding rapidly in Europe and also at the global level, in response to the continuously growing energy demand and because of the high degree of reliability, the easy handling, and the cheap and simple logistics, in comparison to other solid biomasses. The fast growth of this market has highlighted the problem of product quality, which has strong repercussions for technical, environmental, and economic aspects. The biomass quality is defined by several chemical physical parameters that are directly measurable in the laboratory. In addition, there are quality attributes related to origin and source, difficult to investigate through traditional analyses, such as the type of wood (hardwood/softwood) and the presence of bark. The development of a rapid technique able to provide this information could be an advantageous tool for the energy sector proving indications on biofuel traceability and sustainability. More than 90 samples belonging to three of the most common European species for the energy pellet sector (fir, pine, and beech) have been collected and analyzed by means of Fourier transform near-infrared (FT-NIR) coupled with Principal Component Analysis (PCA). The results show that the main variation in the data is due to both differences between bark and wood, as well as differences between hardwood and softwood. The differences are mainly linked to changes in composition and amounts of cellulose, hemicellulose, lignin, and extractives. Moreover, 30 wood/bark blends (2%-20% (w/w)) were analyzed, indicating the ability of the system to recognize blends from pure material. This study has shown that spectroscopy coupled with multivariate data analysis is a useful tool verifying the compliance of producer declarations and assisting experts in evaluation of the biomass quality.