A method for synthesizing graphene derivatives from asphaltene is proposed in this work. The graphene derivatives are mainly composed of few-layer graphene-like nano-sheets of randomly distributed heteroatoms; mainly sulfur and nitrogen. The proposed method is based on a thermal treatment in which asphaltene is carbonized in a rotating quartz-tube furnace under an inert atmosphere at a temperature in the range of 400–950 °C. Asphaltenes from different origins were employed to verify the synthesis method. The results indicate that graphene derivatives obtained at high carbonization temperature have similar structural parameters, despite the evident differences in parent asphaltenes structures and compositions. The transformation of asphaltene to graphene derivatives mainly occurred due to three factors: the reduction in the average number of aromatic layers (n), the expansion in aromatic sheet diameter (L_a), and the elimination of alkyl side chains. The reduction in the number of aromatic sheets per stack is primarily ascribed to thermal exfoliation, while the increase in the aromatic sheet diameter is attributed to secondary reactions in the aromatic core of asphaltene. The elimination of side chains, on the other hand, is mainly credited to thermal cracking. The quantification of defect density (L_D) in the graphene derivatives suggests an association between defects and heteroatoms presence.