This paper presents the theoretical model and the simulation of a cutting edge hybrid power system composed of an externally-fired gas turbine (EFGT) coupled with an organic Rankine cycle (ORC) as a bottoming unit for the maximization of electrical power. The power plant is fed with different biomass sources from olive industry wastes (pruning, dry pomace, stones, leaves and twigs), providing more than 550 kW of electric power and a net electrical efficiency of 26.0%. These wastes were burnt directly at atmospheric pressure in an EFGT, producing 400 kW of electric power and exhaust gases at 300 °C. Ten suitable ORC working fluids have been studied to maximize the electric power generation: cyclohexane, isohexane, pentane, isopentane, neopentane, R113, R245fa, R365mfc, R1233zd and methanol. The best fluid was R1233zd, reaching 152.4 kW and 22.1% of ORC thermal efficiency; as drawback, however, R1233zd was not suitable for Combined Heat and Power CHP applications due its lower condensation temperature. Thus, despite R113 gave minor electricity production (137.5 kW) this allowed to generate additional thermal power (506.8 kW) in the way of hot water at 45 °C.