Ludwigite samples from three boron-bearing magnesian skarns in Romania (Ocna de Fier, Masca-Baisoara and Pietroasa) were used to determine the influence of Al on the main physical and crystallographic constants of this mineral. The selected samples form a minor solid solution towards vonsenite (0.74 to 23.87 mol.%) and have XAl = Al/(Al + Fe3+) ratios between 0.004 and 0.300. Other substitutions, such as those involving Mn, Ni, Co, Ti, Sn, Sb or V are of minor importance. Generally speaking, it is proven that ludwigite shows a negative correlation between XAl and the density, indices of refraction, cell volume and c cell parameter. It is not possible to quantify the variations in the physical and crystallographic parameters by advancing the Al-for-Fe3+ substitution because both Fe2+-for-Mg and Al-for-Fe3+ substitutions are involved. However, it is clear that Al plays a major role in decreasing the cell volume, c cell parameter, density, absorption coefficient, bireflectance and refraction indices of ludwigite. Because of the influence of Al, natural compositional members of the ludwigite-vonsenite series cannot be unambiguously distinguished, neither by their cell dimensions nor by their physical parameters as previously suggested (e.g.,Aleksandrov, 1968; 1982).