It is well known that the alignment of liquid crystals (LCs) can be realised by rubbing or photoalignment technologies. Recently, nonlinear laser lithography (NLL) was introduced as a fast, relatively low-cost method for large area nano-grating fabrication based on laser-induced periodic surface structuring. In this letter for the first time, the usage of the NLL as a perspective method of the alignment of nematics was presented. By NLL, nanogrooves with about 0.92 μm period were formed on Ti layer. The nanostructured Ti layer (NSTL) was coated with oxidianiline-polyimide film with annealing of the polymer followed without any further processing. Aligning properties of NSTLs were examined with combined twist LC cell. The dependencies of the twist angle of LC cells and azimuthal anchoring energy (AE) of layers on scanning speed and power of laser beam during processing of the Ti layer were the focus of our studies as well. The maximum azimuthal AE, obtained for pure NSTL, is comparable with photoalignment technology. It was found that the deposition of polyimide film on NSTL leads to the gain effect of the azimuthal AE. Also, atomic force microscopy (AFM) study of aligning surfaces was carried out.