We report Langmuir-Blodgett (LB) based assembly of vanadium dioxide (VO2) nanowires. VO2 nanowires were functionalized with stearic acid(SA) and cetyltrimethyl ammonium bromide (CTAB) and then spread on the surface an aqueous phase in a LB trough. Surface pressure-area (π-A) isotherms were recorded on the LB trough and show hysteretic behavior. Scanning electron microscopy (SEM) investigations of morphology and alignment of the VO2 nanowire films transferred at different points on the π-A curve demonstrate with increasing surface pressure there is a transition from well-separated domains of nanowires to compact and locally-ordered nanowire monolayers, while aggregates raft-like nanowire structures remain after expansion. Interestingly, X-ray diffraction (XRD) studies show that VO2 nanowire LB films exhibits (00l) crystal plane orientation, which was attributed to preferential coordination of SA and CTAB-SA complex to (001) surface of VO2 nanowires thereby driving this orientation.