Display omitted •A reversible novel reversible HTHP-ORC system was proposed.•Heat source temperature increment benefits the energy performance for both modes.•Built-in volume ratio and IHX effectiveness optimization was realised.•The novel HTHP-ORC provides a COP of 2.44 and net electrical efficiency of 8.75%.•HCFO-1224yd(Z) and HCFO-1233zd(E) are appropriate alternatives for HFC-245fa. Nowadays, a high amount of industrial thermal energy is still lost due to the lack of competitive solutions for energy revalorization. Facing this challenge, this paper presents a novel technology, based on a reversible High-Temperature Heat Pump (HTHP) and Organic Rankine Cycle (ORC). The proposed system recovers low-grade waste heat to generate electricity or useful heat in accordance with consumer demand. Compressor and expander semi-empirical models have been considered for the reversible system computational simulation, being HFC-245fa the working fluid selected. The built-in volume ratio and Internal Heat Exchanger (IHX) effectiveness have been optimized to reach the maximum energy efficiency in each operating condition. Although HFC-245fa exhibits energy performance attributes, its high Global Warming Potential (GWP) is an issue for climate change mitigation. Hence, multi-objective optimisation of the environmentally friendly working fluids Butane, Pentane, HFO-1336mzz(Z), R-514A, HCFO-1233zd(E) and HCFO-1224yd(Z) has been carried out. The results show that the system proposed, working with HFC-245fa, achieves a Coefficient of Performance (COP) of 2.44 for condensing temperature of 140 °C, operating in HTHP mode, whereas the ORC mode provides a net electrical efficiency of 8.7% at condensing temperature of 40 °C. Besides, HCFO-1233zd(E) and HCFO-1224yd(Z) are both appropriate alternatives for the HFC-245fa replacement. These working fluids provide a COP improvement of 9.7% and 5.8% and electrical net efficiency improvement of 2.1% and 0.8%, respectively, compared to HFC-245fa. This paper provides a reference study for further designs and developments of reversible HTHP-ORC systems used for industrial low-grade waste heat recovery.