Graphene is a unique material with outstanding mechanical and electronic properties. For solution processes graphene layers have to be stabilized by means of molecular or supramolecular chemical derivatization, prior to their transfer to solid substrates. The most common chemical methodology for the preparation of graphene involves the formation of graphene oxide under highly oxidizing conditions, which even after reduction, lacks the electronic quality of pristine graphene. Presently, there is increasing concern in the chemical community about the starting material quality, and recent efforts are directed to wet chemical approaches toward high-quality graphene flakes which encompass the use of graphite as initial material. In addition, epitaxial growth of graphene on metallic surfaces is becoming a powerful technique for the production of pristine graphene with a control on its electronic properties, somehow due to the supramolecular interaction with the metallic surface. Current approaches for the preparation of modified pristine graphene are the aim of this review.