The interactions of l-arginine (l-arg) with Langmuir monolayers of three most common phospholipids, which are sodium salt of dipalmitoylphosphatidylglycerol (DPPG), dipalmitoylphosphatidylcholine (DPPC) and dipalmitoylphosphatidylethanolamine (DPPE), have been investigated at the air-water interface. The surface pressure-area (π-A) isotherms of these monolayers have been measured with a film balance and monolayer morphology has been observed by a Brewster angle microscopy (BAM). The DPPG monolayers on pure water do not show any phase transition but show irregular shaped condensed phases formed just after evaporation of the solvent at 20 °C. However, this monolayer on l-arg solution subphase indicates a first-order phase transition from liquid expanded to liquid condensed (LE-LC) phases and forms LC domains at the same temperature. With an increase in the l-arg concentration in the subphase up to 5.0 × 10-4 M, the π-A shows an overall increasingly greater expansion in the molecular area. All of the π-A isotherms recorded on ≥5.0 × 10-4 M l-arg solution subphases almost coincide with each other. These changes in the phase behavior have been explained by the fact that l-arg having guanidinium cationic group undergoes strong hydrogen bonding interaction with the anionic phosphatidylglycerol (PG-) head group. The bonding between two molecules is further strengthened by electrostatic attraction between cationic l-arg and anionic PG- ions. The BAM observation of the monolayer morphology supports this explanation. On the other hand, a very negligible interaction has been observed between l-arg and DPPC or DPPE monolayers. The π-A isotherms in the presence of l-arg for both the amphiphiles show a very little expansion only in the LE phase region, but coincide in the so called solid phase region. The monolayer morphology of both the monolayers also supports these results. This little effect of expansion in the LE region may be explained by the ion-pair formation between cationic l-arg and anionic head groups in the monolayers at lower pressures. However, due to compression at high pressure, the l-arg molecules are squeezed out from the amphiphile head groups.