Graphene oxide (GO) is promising for a variety of applications due to its excellent dispersibility and processability. However, current chemical oxidation routes have several drawbacks, including the use of explosive oxidizing agents, residual metal ions contaminations, and the creation of irreparable hole defects on the GO sheet. The electrochemical exfoliation and oxidation of graphite is a potentially greener approach without the need for extensive purification steps. Most reported electrochemical methods employ a single preformed bulk graphite as electrode, which limits their scalability, reproducibility, and degree of oxidation. Herein, we reported a novel mechanically assisted electrochemical method to produce graphene oxide directly from graphite flakes. The electrochemically derived graphene oxide (EGO) shows a good degree of oxidation but with less physical defects than chemically derived graphene oxide (CGO). EGO has good dispersibility in water and various solvents and, in particular, displays better long-term stability in ethanol when compared with CGO. Notably, unlike conventional CGO, EGO can undergo facile thermal conversion at 200 °C in air to conductive thermally processed EGO, which is highly desirable for heat/chemical-sensitive applications.