Hyperspectral image processing techniques, with their ability to provide information about the chemical compositions of materials, have great potential for pavement condition assessment. This study introduces a novel age-based pavement assessment method, employing an integrated algorithm with artificial neural network (ANN) and spectral angle mapping (SAM) on hyperspectral images. In the proposed method, the resulting ANN prediction outputs are used to make a new prediction along with the results from SAM scores. Tests are performed on hyperspectral images that have 360 spectral bands between 400 and 900 nm, collected by a specifically designed vehicular system for proximal image acquisition. The acquired images have eight classes, including three different pavement classes (good (5-year), medium (10-year), and poor (25-year)), yellow dye, white dye, soil, paving stone, and shadow. Several experiments are performed to evaluate the robustness of the followed methodology with limited learning data that include 5, 10, 25, and 50 samples per class, selected randomly from our independent spectral database. For a fair comparison, the individual ANN, SAM, support vector machine (SVM), and stacked auto-encoders (SAE) algorithms are also evaluated. The classification performances of individual ANN and SAM are significantly increased with their joint use, demonstrating a 1.2% to 21% classification accuracy improvement in relation to the training sample size. The study proves that the proposed approach is quite robust in cases wherein few training data are available, while SAE and standard ANN algorithms are more successful in cases wherein more learning data are present.