Langmuir and Langmuir-Blodgett (LB) films of non-amphiphilic 2-(4-Biphenylyl)-5-phenyl-1,3,4-oxadiazole (abbreviated as PBD) mixed with stearic acid (SA) as well as with the inert polymer matrix poly(methyl methacrylate) (PMMA) have been studied. Surface pressure versus area per molecule (p-A) isotherm studies suggest that PBD molecules very likely stand vertically on the air-water interface and this arrangement allows the PBD molecules to form stacks and remain sandwiched between SA/PMMA molecules. At lower surface pressure, phase separation between PBD and matrix molecules occurs due to repulsive interaction. However, at higher surface pressure, PBD molecules form aggregates. The UV-vis absorption and steady-state fluorescence spectroscopic studies of the mixed LB films of PBD reveal the nature of the aggregates. H-type aggregate predominates in the mixed LB films, whereas I-type aggregate predominates in the PBD-PMMA spin-coated films. The degree of deformation produced in the electronic levels are largely affected by the film thickness and the surface pressure of lifting. r 2007 Published by Elsevier B.V.