Phosphorene, a single‐ or few‐layered semiconductor material obtained from black phosphorus, has recently been introduced as a new member of the family of two‐dimensional (2D) layered materials. Since its discovery, phosphorene has attracted significant attention, and due to its unique properties, is a promising material for many applications including transistors, batteries and photovoltaics (PV). However, based on the current progress in phosphorene production, it is clear that a lot remains to be explored before this material can be used for these applications. After providing a comprehensive overview of recent advancements in phosphorene synthesis, advantages and challenges of the currently available methods for phosphorene production are discussed. An overview of the research progress in the use of phosphorene for a wide range of applications is presented, with a focus on enabling important roles that phosphorene would play in next‐generation PV cells. Roadmaps that have the potential to address some of the challenges in phosphorene research are examined because it is clear that the unprecedented chemical, physical and electronic properties of phosphorene and phosphorene‐based materials are suitable for various applications, including photovoltaics.