The article presents modified Pd-based catalysts supported on reduced graphene oxide (rGO), used in the electrooxidation reaction of ethanol in alkaline medium. When NaBH₄ reducing agent was used, the random presence of Na was found out. According to this result, Na was used as a promoter of Pd-based catalyst. Consequently, the Al-Si-Na addition not only assisted active phase Pd nanoparticles to disperse homogenously on graphene surport, but also contributed to increase catalytic activity in the reaction. This value, 16138 mA·mg⁻¹_Pd, is about 1.5 times higer than that of the catalyst modified by Al-Si. Moreover, the stability of the catalyst is enhanced more. The electrochemical stability of PASGN.N catalyst was relatively good: after 500 scanning cycles, the current density diminished 32% compared with the highest peak current density of the 15^th cycle, which was chosen as a reference. These significant improvement results in electrooxidation of ethanol have opened up the high potential application of these catalysts in direct-ethanol fuel cell.