Three-dimensional graphene (3DG) with macroporous structure has great potential in the field of electroanalysis owing to a large active area, excellent electron mobility and good mass transfer. However, simple and low-cost preparation of 3DG electrodes with high electrocatalytic ability is still a challenge. Here, a fast and convenient electrochemical polarization method is established to pretreat free-standing 3DG (p-3DG) to offer high electrocatalytic ability.