Imaging ellipsometry is an optical characterization tool that is widely used to investigate the spatial variations of the opto-geometrical properties of thin films. As ellipsometry is an indirect method, an ellipsometric map analysis requires a modeling step. Classical methods such as the Levenberg–Marquardt algorithm (LM) are generally too time consuming to be applied on a large data set. In this way, an artificial neural network (ANN) approach was introduced for the analysis of an ellipsometric map. As a proof of concept this method was applied for the characterization of silver nanoparticles embedded in a poly-(vinyl alcohol) film. We demonstrate that the LM and ANN give similar results. However, the time required for the ellipsometric map analysis decreases from 15 days for the LM to 1 s for the ANN. This suggests that the ANN is a powerful tool for fast spectroscopic-ellipsometric-imaging analysis.