Structured light is attracting significant attention for its diverse applications in both classical and quantum optics. The so-called vector vortex beams display peculiar properties in both contexts due to the nontrivial correlations between optical polarization and orbital angular momentum. Here we demonstrate a new, flexible experimental approach to the classification of vortex vector beams. We first describe a platform for generating arbitrary complex vector vortex beams inspired to photonic quantum walks. We then exploit recent machine learning methods-namely, convolutional neural networks and principal component analysis-to recognize and classify specific polarization patterns. Our study demonstrates the significant advantages resulting from the use of machine learning-based protocols for the construction and characterization of high-dimensional resources for quantum protocols.