Using Langmuir and Langmuir-Blodgett techniques molecular films of chlorinated perylene derivatives, namely tetra-n-butyl-1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxylate (PCn for n = 1, 5, 9) have been studied. The Langmuir films of pure compounds and mixed with liquid crystalline 4-octyl-4′-cyanobiphenyl (8CB) were characterized by surface pressure-mean molecular area isotherms. An additive rule reveals miscibility of all the dyes with 8CB but shows different types of intermolecular interaction forces. The pure and mixed Langmuir films were transferred onto quartz plates and characterized spectroscopically. Absorption and fluorescence spectra were recorded for the samples in form of diluted chloroform solution, the dye with 8CB mixtures in monomolecular Langmuir-Blodgett films and in liquid crystal cells. Different tendency to aggregation of the dye with short and long alkyl chains was observed. It is shown that the dye molecule stacking and aggregation of the chlorinated perylene dyes depend on the dye concentration and are related to the torsion of the perylene core.