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The rapid technological progress in the 21 st century demands new multi-functional materials applicable to a wide variety of industries. Two-dimensional (2D) materials are predicted to have a revolutionary impact on the cost, size, weight, and functions of future electronic and optoelectronic devices. Graphene, which shows potential as an alternative to conventional conductive transparent metal oxides, may play a central role. Since its work function (WF) is tunable, graphene exhibits the interesting ability to serve two different roles in electronic and optoelectronic devices, both as an anode and a cathode.After introducing some basic concepts, this work reviews the most important advances in controlling the tuned WF of graphene, highlighting special features of graphene electronic band structure and recognizing different methods for measuring WF. The impact of thickness, type of contact, chemical doping, UV and plasma treatments, defects, and functional groups of graphene oxide are considered and related with the applications of the modulated material. The results of the review, organized in lookup tables, have been used to identify the advantages and main challenges of the tuning methods.