N-Salicylideneaniline (SA), C13H11NO, belongs to the large family of aromatic Schiff bases. It is of particular importance owing to its reversible photoreactivity. SA forms two photochromic polymorphs, both with two non-coplanar benzene rings. In addition, we have recently discovered a planar polymorph, named the β-polymorph, which will be discussed in a subsequent paper. We report here the structure of the α(2)-polymorph in the orthorhombic crystal system. This compound exhibits a strong intramolecular O-H••• N hydrogen bond and the dihedral angle between the two rings varies with temperature.