We report on the formation of high aspect ratio anisotropic nanopatterns on crystalline GaAs (100) and Si (100) substrates exploiting defocused Ion Beam Sputtering assisted by a sacrificial self-organised Au stencil mask. The tailored optical properties of the substrates are characterised in terms of total reflectivity and haze by means of integrating sphere measurements as a function of the morphological modification at increasing ion fluence. Refractive index grading from sub-wavelength surface features induces polarisation dependent anti-reflection behaviour in the visible-near infrared (VIS-NIR) range, while light scattering at off-specular angles from larger structures leads to very high values of the haze functions in reflection. The results, obtained for an important class of technologically relevant materials, are appealing in view of photovoltaic and photonic applications aiming at photon harvesting in ultrathin crystalline solar cells.