Abstract The surfactant molecules at a Langmuir monolayer interact with each other via both hydrophobic and hydrophilic interactions. The interplay between those molecular interactions leads to the molecular arrangement of the monolayer. Herein, a new type of inorganic/organic surfactant in which the interactions between the polar headgroups are dominant is combined with a linear alkane. The hydrophobic interactions are enhanced, leading to an ordered state of the hydrocarbon chains. The crystalline ordering of the chains is identified by synchrotron grazing incidence X-ray diffraction (GIXD). The molecular arrangement described herein might serve as a starting point for the design of ordered inorganic/organic hybrids that assemble efficiently at interfaces.