To explore offshore oil fields in deepwater, the use of a floating production storage and offloading (FPSO) unit coupled to a shuttle tanker is economically and technically feasible. Shuttle tankers like system for oil transportation are increasingly being accepted as a preferred transportation method for remote and deepwater offshore developments. The offloading operation is considered one of the riskiest operations in offshore environment. The chapter presents a risk-based analysis method aiming at defining the risk profile associated with an offloading operation. For offloading operations, the risk profile is usually evaluated considering that the offloading operation has an approximate duration of 24 hours. The method follows three basic steps: identification of hazard, definition of failure scenarios and their probability of occurrence, and evaluation of failure consequences. The decision-making theory is used to evaluate the possibility of emergency disconnection during the operation. The method is applied to evaluate the risk profile of an offloading operation in Campos Basin, Brazil, considering a FPSO moored with Differentiated Complacent Anchoring System (DICAS). The method is used to model the risk scenario associated with shuttle tanker main engine failure as initiating event. The changes in environmental conditions have great influence in risk profile and increase the probability of disconnection.