Monolayers on mica of two rigid amphiphiles of specific cross-sectional geometry have been studied by atomic force microscopy and are ordered over micron scale areas. An interlocking amphiphile shows disruption into crystalline shards on transfer from the aqueous subphase. A chiral amphiphile retains its integrity when transferred from the intermediate pressure phase but exhibits catastrophic changes when transferred from the high pressure phase. The results imply that the interlocked amphiphile has the same structure for both aqueous and solid subphases. The phases exhibited by the chiral amphiphile on mica are probably not those observed on the aqueous subphase.