We monitored single-layer Langmuir-Blodgett films of behenic acid deposited on silanized glass or silicon substrates by atomic force microscopy (AFM) in liquid. We observed the in situ transformation of the monolayer to a bilayer when the surrounding solution was NaOH or KOH with pH > 8.3. The final state is that of an inverted bilayer, in which both the hydrophobic OTS (octadecyltrichlorosilane) and the alkane chains are exposed to the surrounding solution, defying common intuition based on hydrophobic-hydrophilic energy considerations. Strong sodium-containing carboxylic dimers formed between the headgroups are shown to be responsible for the stabilization of this configuration; calcium ions slow down/inhibit the transformation.