There is an increasing gap between the needs of modern, complex, and distributed environments in regards to control of access to data and the level to which classical access control solutions can fulfill those needs. The purpose of this chapter is to highlight the current state of art of existing research over access control in increasingly decentralized environments and to argue how the subject of access control is more relevant than ever before, with increasing research opportunities emerging. In this chapter, the authors analyze the current state of the art of access control mechanisms and systems over decentralized applications with a focus on enterprise ecosystems, analyze the current challenges and opportunities that the new technological landscape offers, specifically over the application of blockchain-based technologies in access control, and propose new research directions for the future.