We study the surface structure of Sb-terminated singular (on-axis) and vicinal (4 degrees offcut in [110]) Si(001) by Raman spectroscopy (RS). In the Raman spectra three surface phonons with A(1)-symmetry are identified at 80 cm(-1), 130.5 cm(-1) and 162 cm(-1). The polarisation dependent Raman scattering intensities for the singular and vicinal samples are found to be correlated with the different surface reconstructions. After deposition of Sb at 260 degrees C and further annealing to 400 degrees C and 600 degrees C, a nearly balanced ratio of (2 x 1):(1 x 2) domains for the singular sample and a predominantly (2 x 1) reconstructed surface for the vicinal sample is derived from RS, in agreement with LEED results. In contrast, after Sb deposition at 600 degrees C, a balanced ratio of (2 x 1) and (1 x 2) reconstructed domains is found for vicinal as well as for singular Si(001).