The generation of super-high energetic electrons influenced by pre-plasma in relativistic intensity laser–matter interaction is studied in a one-dimensional slab approximation with particle-in-cell simulations. Different pre-plasma scale lengths and laser intensities are considered, showing an increase in both particle number and cut-off kinetic energy of electrons with the increase of pre-plasma scale length and laser intensity, the cut-off kinetic energy greatly exceeding the corresponding laser ponderomotive energy. A two-stage electron acceleration model is proposed to explain the underlying physics. The first stage is attributed to the synergetic acceleration by longitudinal electric field and counter-propagating laser pulses, and a scaling law is obtained with efficiency depending on the pre-plasma scale length and laser intensity. These electrons pre-accelerated in the first stage could build up an intense electrostatic potential barrier with maximal value several times as large as the initial electron kinetic energy. Some of the energetic electrons could be further accelerated by reflection off the electrostatic potential barrier, with their finial kinetic energies significantly higher than the values pre-accelerated in the first stage.