We have fabricated pure and mixed, mono- and multilayer Langmuir Blodgett (LB) films from the long chain amphiphiles ferric stearate (FS) and stearonitrile (SN). These films deposit in either a head-to-head, tail-to-tail (Y-type) fashion or with a head-to-tail (Z-type) architecture depending upon the film composition. We have employed the techniques of sum frequency generation (SFG) vibrational spectroscopy and scanning probe microscopy to examine the averaged orientation of the amphiphiles and the structural order within these films. Our results indicate that for LB films of composition >65% stearonitrile, the LB films deposit with a head-to-tail architecture, while for compositions <65% stearonitrile, the films deposit head-to-head and tail-to-tail. SFG experiments show significant differences in the alkyl chain orientations depending upon film architecture, while atomic force microscopy indicates a high degree of order between the amphiphile chains, regardless of film architecture. We discuss these results and their implications on the nature of surface wettability at the molecular scale.