New and innovative separation method was developed for extraction of molybdenum(VI) from aqueous chloride media with N-n-octylaniline (liquid anion exchanger) coated on silica gel. Molybdenum(VI) was quantitatively extracted from 1.25 M HCl, eluted with distilled water and determined by spectrophotometric method. Different parameters viz, effect of HCl concentration, N-n-octylaniline concentration and flow rate of mobile phase were studied. The method was applied for separation of molybdenum(VI) from binary mixtures and synthetic mixtures corresponding to alloys and fertilizer samples.