Major accidents involving hazardous materials are a crucial issue for the chemical and process industries. Many accidental events taken place in the past showed that dangerous substances may pose a severe threat for people and property. Aiming at loss prevention, a series of actions have been instituted through international regulations concerning hazardous installations safety preparedness. These actions involve efficient land-use planning, safety studies execution, as well as emergency response planning drawing up. A key factor for the substantial consideration of the above is the effective prediction of possible accident forms and their consequences, for the estimation of which, a number of empirical models have been developed so far. However, (semi-)empirical models present certain deficiencies and obey to certain assumptions, thus leading to results of reduced accuracy. Another approach that could be used for this purpose and it is discussed in this work, is the utilization of advanced computational fluid dynamics (CFD) techniques in certain accident forms modeling. In particular, composite CFD-based models were developed for the simulation of several characteristic accident forms involving isothermal and non-isothermal heavy gas dispersion, confined and unconfined explosion in environment of complex geometry, as well as flammable cloud fire. The simulation cases were referred to real-scale trials allowing us to conclude about the validity of the quantitative results. Comparisons of the computational predictions with the experimental observations showed that obtained results were in good agreement with the experimental ones, whereas the evaluation of statistical performance measures proved the simulations to be statistically valid. (C) 2011 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.