Langmuir monolayers of a homologous series of perfluorododecyl-n-alkanes (general formula F(CF2)(12)(CH2)(n)H, abbreviated as F12Hn, where n = 6-20) are investigated through isotherms of surface pressure (pi) and electric surface potential (AV) versus area (A) and quantitative Brewster angle microscopy. The investigated monolayers are found to be liquid in nature. The negative sign of the measured surface potential evidences the orientation of all the investigated molecules with their perfluorinated parts directed toward the air regardless of the length of the hydrogenated unit. Analysis of the direction of the molecular dipole moment with respect to the main axis indicates that the minimum effective dipole moment is achieved for a molecule oriented at an angle of about 35degrees to the surface normal. The film thickness was evaluated from the relative intensity measurements. The results suggest that the F12Hn molecules are tilted to the interface in the vicinity of collapse, which is in accordance with the liquid character of their monolayers. (C) 2004 Published by Elsevier Inc.