The aim of this article is to investigate some implications of complexity in workplace risk assessment. Workplace is examined as a complex system, and some of its attributes and aspects of its behavior are investigated. Failure probability of various workplace elements is examined as a time variable and interference phenomena of these probabilities are presented. Potential inefficiencies of common perceptions in applying probabilistic risk assessment models are also discussed. This investigation is conducted through mathematical modeling and qualitative examples of workplace situations. A mathematical model for simulation of the evolution of workplace accident probability in time is developed. Its findings are then attempted to be translated in real-world terms and discussed through simple examples of workplace situations. The mathematical model indicates that workplace is more likely to exhibit an unpredictable behavior. Such a behavior raises issues about usual key assumptions for the workplace, such as aggregation. Chaotic phenomena (nonlinear feedback mechanisms) are also investigated for in simple workplace systems cases. The main conclusions are (1) that time is an important variable for risk assessment, since behavior patterns are complex and unpredictable in the long term and (2) that workplace risk identification should take place in a holistic view (not by work post).