An effective safety management requires attention to human factors as well as system components which make risky or safe situations at technical components. This study evaluates and analyze ergonomic behaviors in order to select the best work shift group in an Iranian process industry, in 2010.The methodology was based on the Ergonomic Behavior Sampling (EBS), and TOPSIS method. After specifying the unergonomic behaviors and with reference to the results of a pilot study, a sample of 1755 was determined, with a sampling accuracy of 5% and confidence level of 95%. However, in order to gain more confidence, 2631 observations were collected. The results indicate that 43.6% of workers' behaviors were unergonomic. The most frequent unergonomic behavior was amusing of legs while load lifting with 83.01% of total unergonomic behaviors observations. Using TOPSIS method, the most effective shift group and the least attractive alternatives for intervention were selected in this company. Findings declare high number of unergonomic behaviors. Catastrophic consequences of accidents in petrochemical industry necessitate attention to workers' ergonomic behaviors in the workplace and promotion of them.