The molecular architecture of polymeric films can be changed in order to obtain enhanced properties for the fabrication of optoelectronic devices. In this paper, poly(2-chloro-p-phenylenevinylene) was spread on the air-water interface and mixed with stearic acid in order to form stable Langmuir monolayers. These films were transferred from the air-water interface to solid supports as Langmuir-Blodgett (LB) films. The influence of Cl in the polymer chain was investigated with measurements of surface pressure, polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS), Brewster angle microscopy (BAM), atomic force microscopy (AFM), and fluorescence spectroscopy. The immobilization of this polymer on solid supports as LB films provided a high control of its morphological and luminescence properties, which may be useful to manipulate structures at the molecular level to be applied as optoelectronic devices.Graphical abstractCl-PPV was co-spread with stearic acid at the air-water interface and transfer to solid supports as Langmuir-Blodgett films.