The non-Oberbeck–Boussinesq effects on the stability of a vertical natural convection boundary layer are investigated using the linearised disturbance equations for air flows up to a temperature difference of $\Delta T=100\,{\rm K}$ . Based on the linear stability results, the neutral curve is shown to be sensitive to the choice of reference temperature. When evaluated using the film temperature $T_f$ , a lower film Grashof number is required to trigger the linear instability for larger $\Delta T$ . The relative contributions of shear and buoyant production to the perturbation kinetic energy budget reveals that the marginally unstable modes are amplified based on different mechanisms: for lower wavenumbers at relatively small Grashof number, the instability is driven by buoyancy; whereas for higher wavenumbers and larger Grashof number, the flow becomes unstable due to a shear instability. The use of reference temperature is found to scale the shear- and buoyant-driven instabilities differently so that no single reference temperature definition would collapse the neutral curves. The linear stability result further demonstrates that at a given Grashof number a higher temperature difference would give a larger amplification rate of the perturbation, which then leads to an earlier onset of the nonlinearities when evaluated at $T_f$ . Finally, by comparing the amplification rates obtained from direct numerical simulation and the linear stability results, the extent of the linear regime is determined for $\Delta T = 100\,{\rm K}$ .