A hybrid technique is proposed to enhance the localization performance of a time difference of arrival (TDOA) deployed in non-line-of-sight (NLOS) suburban scenario. The idea was to use Machine Learning framework on the dataset, produced by the ray tracing simulation, and the Channel Impulse Response estimation from the real signal received by each sensor. Conventional localization techniques mitigate errors trying to avoid NLOS measurements in processing emitter position, while the proposed method uses the multipath fingerprint information produced by ray tracing (RT) simulation together with calibration emitters to refine a Machine Learning engine, which gives an extra layer of information to improve the emitter position estimation. The ray-tracing fingerprints perform the target localization embedding all the reflection and diffraction in the propagation scenario. A validation campaign was performed and showed the feasibility of the proposed method, provided that the buildings can be appropriately included in the scenario description.