In this paper, we present a detailed theoretical analysis of charge exchange recombination spectroscopy based on interactions of the planned ITER neutral beams (diagnostic beam of 100 keV u−1 and heating beam of ≈1 MeV u−1) with highly-charged ions of tungsten. The results of the present spectral synthesis are based on the new set of nl-resolved charge exchange (CX) cross sections for recombination of the W ions (q = 61–66) with atomic hydrogen calculated using the classical trajectory Monte Carlo method. A large-scale collisional-radiative model describing the population kinetics of the high-n atomic states of Si-like through O-like W ions has been developed using the NOMAD code for typical conditions of the ITER core plasma, and the resulting spectra have been generated for wavelengths in the x-ray to visible range (0.1–1000 nm). A detailed analysis of the plasma emission predicts a significant effect of CX recombination on the W line intensity ratios that can be used for more advanced diagnostics of the ITER plasma.