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One of the most widely used demand response programs is Time of Use (TOU) pricing. Using proper tariffs for different load periods (peak, off-peak and middle periods) is vitally important for the implementation of TOU program. In this research, using demand response model, two new methods for optimal pricing of TOU program are proposed. In this regard, the optimal tariff for each period is determined through solving an optimization problem. In addition, we comprehensively investigate the effect of TOU program on the Load Duration Curve (LDC) using an analytical DR model.