Abstract <p>Films consisting of arrays of MoS₂ crystallites (nanowalls), which are oriented perpendicular to the substrate, attract the attention of researchers as a promising material for creating photonic, optoelectronic, and sensor devices. The additional ordering of the structure of such layers by orientating nanowalls along a certain direction in the substrate plane allows creation of materials with unique characteristics. For their formation, we use the method of selective laser ablation of MoS₂ films formed via deposition from the vapor phase and consisting of nanowalls on the surfaces of silicon substrates. The parameters of a laser pulse, which lead to the emergence of the maximum degree of ordering of nanowalls in the film, are determined. The photoluminescence (PL) and Raman scattering (RS) have been studied. In particular, the degree of polarization of PL and RS signals was determined as a function of the angle between a selected direction in the film plane and the polarization of exciting radiation. It was revealed that exactly nanowalls are responsible for the optical properties of such films but not the underlying film. The possible applications of the materials obtained using the selective ablation method in photonics are discussed.</p>