Electrochemically exfoliated graphene (EEG) possesses optical and electronic properties that are markedly different from those of the more explored graphene oxide in both its pristine and reduced forms. EEG also holds a unique advantage compared to other graphenes produced by exfoliation in liquid media: it can be obtained in large quantities in a short time. However, an in-depth understanding of the structure-properties relationship of this material is still lacking. In this work, we report physicochemical characterization of EEG combined with an investigation of the electronic properties of this material carried out both at the single flake level and on the films. Additionally, we use for the first time microwave irradiation to reduce the EEG and demonstrate that the oxygen functionalities are not the bottleneck for charge transport in EEG, which is rather hindered by the presence of structural defects within the basal plane.