•Nano γ–alumina (20 nm) was first reported for Al2O3 PLOT column.•Highly performance and good selectivity different with either bulk or commercial alumina columns.•Easily coated with dynamic method under relative lower coating pressure.•Film thickness could be tuned by coated again, which was not possible on bulk alumina.•The γ crystallite structure and size remained constant of nano γ–alumina whereas specific surface area, pore volume and average half pore width changed obviously. An alumina porous layer open-tubular (Al2O3 PLOT) column coated with γ–alumina nanoparticles (20 nm) for highly volatile hydrocarbons (C1 to C5) separation was described. Relative to the coating of bulk alumina, this column was easily coated with dynamic method under 0.4 or 0.6 MPa for 0.53 mm or 0.32 mm capillary, respectively. And the thickness of coating layer could be tuned by repeating the coating process after column was dried and activated at 300 °C for 3 h. The effect of deactivation agents on the physicochemical properties of nano γ–alumina was characterized by X–ray diffraction (XRD) measurement and nitrogen adsorption–desorption isotherms. The influences of deactivation agents, film thickness, conditioning and column dimensions on the inertness, polarity, selectivity and elution order of C1 to C5 separation were investigated in detail. The crystallite structure and size of nano alumina were not affected by the deactivation agents and remained constant during the column making processes, whereas specific surface area, pore volume and average half pore width altered significantly. The specific surface area decreased to 125.4 m2 g–1 or 174.0 m2 g–1 and the average half pore size distributions decreased to 1.6–8.4 nm or 2.4–14.3 nm when it was deactivated with potassium chloride or sodium sulfate solution, respectively. The deactivation agents and its concentrations impacted significantly on the retention performance of column. The column deactivated with sodium sulfate solution exhibited stronger polarity and lower selectivity than which deactivated with potassium chloride solution although both columns showed good inertness. The length, internal diameter and film thickness of the column had less influence on the selectivity and resolution for C1 to C5 hydrocarbons separation, whereas the conditioning temperature and time had an obvious influence. The column had distinguished polarity and selectivity which was different from either bulk or commercial alumina columns. Typically, the hydrocarbons were baseline separated with resolutions ranging from 1.65 to 15.33 within 9 min under programmed temperature below 100 °C, and the tailing factors ranging from 1.02 to 1.07. Display omitted