The study of liquid-liquid phase transitions has attracted considerable attention. One interesting example of this phenomenon is phosphorus, for which the existence of a first-order phase transition between a low density insulating molecular phase and a conducting polymeric phase has been experimentally established. In this Letter, we model this transition by an ab initio quality molecular dynamics simulation and explore a large portion of the liquid section of the phase diagram. We draw the liquid-liquid coexistence curve and determine that it terminates into a second-order critical point. Close to the critical point, large coupled structure and electronic structure fluctuations are observed.