A smart hybrid power plant comprising a waste-fired CHP (combined heat and power) plant accompanied by a small-scale organic Rankine cycle was recently designed and analyzed thermodynamically. The objective of this hybridization is to maximize the share of electricity production of waste-CHP plants rather than a higher heat production rate in a cost-effective manner. In this work, utilization of the exergy of the hot flue gas of the waste-fired CHP unit in order to increase the potential of the organic Rankine cycle for maximizing the net power output of the hybrid cycle is proposed and techno-economically analyzed. In addition, the effect of using alternative environmentally-friendly organic working fluids on the performance of the system was investigated. The results of the study show that by the flue gas potential utilization of the same CHP unit, the size of the organic Rankine cycle may increase significantly, leading to a larger power output of the plant. As such, the net exergy and energy efficiency values of the combined plant in various operational conditions are improved compared to its primary configuration by, respectively, about 10% and 20%, when both of the main CHP cycle and the organic Rankine cycle are working at nominal load. In addition, this exergy utilization is beneficial economically as well, decreasing the payback period of the parallelization project by about 10% (from 7.4 years to 6.7 years). The alternative organic working fluid does not make a significant change in the technical and economic performance indices of the system.