A dual toll pricing is a conceptual policy in which policy maker imposes toll on both hazardous materials (hazmat) vehicles as well as regular vehicles for using populated road segments to mitigate a risk of hazmat transportation. It intends to separate the hazmat traffic flow from the regular traffic flow via controlling the dual toll. In order to design the dual toll pricing policy on a highly realistic road network environment and detailed human behaviors, an extended Belief-Desire-Intention (BDI) framework is employed to mimic human decision behaviors in great detail. The proposed approach is implemented in AnyLogic agent based simulation software with using a traffic data of Albany, NY. Also, search algorithms in OptQuest are used to determine the optimum dual toll pricing policy which results in the minimum risk and travel cost based on the simulation results. The result reveals the effectiveness of the proposed approach in devising a reli-able policy under the realistic road network conditions.