The aim of this work was to recognize different polymer flakes from mixed plastic waste through an innovative hierarchical classification strategy based on hyperspectral imaging, with particular reference to low density polyethylene (LDPE) and high-density polyethylene (HDPE). A plastic waste composition assessment, including also LDPE and HDPE identification, may help to define optimal recycling strategies for product quality control. Correct handling of plastic waste is essential for its further “sustainable” recovery, maximizing the sorting performance in particular for plastics with similar characteristics as LDPE and HDPE. Five different plastic waste samples were chosen for the investigation: polypropylene (PP), LDPE, HDPE, polystyrene (PS) and polyvinyl chloride (PVC). A calibration dataset was realized utilizing the corresponding virgin polymers. Hyperspectral imaging in the short-wave infrared range (1000–2500 nm) was thus applied to evaluate the different plastic spectral attributes finalized to perform their recognition/classification. After exploring polymer spectral differences by principal component analysis (PCA), a hierarchical partial least squares discriminant analysis (PLS-DA) model was built allowing the five different polymers to be recognized. The proposed methodology, based on hierarchical classification, is very powerful and fast, allowing to recognize the five different polymers in a single step.