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Time-of-flight Rutherford backscattering spectroscopy (ToF-RBS) with incident heavy ions offers a substantially improved depth resolution compared to conventional RBS with incident He ions. The new Garching ToF-RBS detector is located at a scattering angle of 150° with a free flight path of 1.313 m and a time resolution of 600 ps. The experimentally achieved depth resolution at the surface of W-containing Fe samples is 2–3 nm using incident Si ions. Model systems consisting of Fe layers with 0.7, 1.5 and 4.2 at% W and EUROFER steel (containing 0.34 at% W + Ta) were eroded by 200 eV D ions to a fluence of 1023 D/m2 at 310 K and 900 K. W depth profiles were measured using ToF-RBS, light impurities at the surface were detected using time-of-flight elastic recoil detection analysis (ToF-ERDA). The data sets from the two techniques were analyzed self-consistently. In all cases W enrichment at the surface was observed. The enrichment at 310 K is in good agreement with SDTrimSP simulations if the experimentally achieved depth resolution is taken into account. Annealing of the model systems with 0.7 and 1.5 at% W to 900 K for 10 h in vacuum resulted also in a W-enriched surface layer. Keywords: Rutherford Backscattering Spectroscopy, RBS, ToF-RBS, Tungsten surface enrichment, EUROFER, MultiSIMNRA