In outdoor RF localization systems, particularly where line of sight can not be guaranteed or where multipath effects are severe, information about the terrain may improve the position estimate’s performance. Given the difficulties in obtaining real data, a ray-tracing fingerprint is a viable option. Nevertheless, although presenting good simulation results, the performance of systems trained with simulated features only suffer degradation when employed to process real-life data. This work intends to improve the localization accuracy when using ray-tracing fingerprints and a few field data obtained from an adverse environment where a large number of measurements is not an option. We employ a machine learning (ML) algorithm to explore the multipath information. We selected algorithms random forest and gradient boosting; both considered efficient tools in the literature. In a strict simulation scenario (simulated data for training, validating, and testing), we obtained the same good results found in the literature (error around 2 m). In a real-world system (simulated data for training, real data for validating and testing), both ML algorithms resulted in a mean positioning error around 100 ,m. We have also obtained experimental results for noisy (artificially added Gaussian noise) and mismatched (with a null subset of) features. From the simulations carried out in this work, our study revealed that enhancing the ML model with a few real-world data improves localization’s overall performance. From the machine ML algorithms employed herein, we also observed that, under noisy conditions, the random forest algorithm achieved a slightly better result than the gradient boosting algorithm. However, they achieved similar results in a mismatch experiment. This work’s practical implication is that multipath information, once rejected in old localization techniques, now represents a significant source of information whenever we have prior knowledge to train the ML algorithm.