Small-CHP (Combined Heat and Power) systems are generally considered a valuable technological option to the conventional boilers, in a technology developed context. If small-CHP systems are associated with the use of renewable energies (biomass, for example) they could play an important role in distributed generation even in developing countries or, in any case, where there are no extensive electricity networks. Traditionally the considered heat engines for micro- or mini-CHP are: the gas engine, the gas turbine (with internal combustion), the steam engine, engine working according to the Stirling and to the Rankine cycles, the last with organic fluids. In principle, also fuel cells could be used. In this paper, we focus on small size Rankine cycles (10–15 k W ) with organic working fluids. The assumed heat source is hot combustion gases at high temperature (900–950 ∘ C ) and we assume to use only single stages axial turbines. The need to work at high temperatures, limits the choice of the right organic working fluids. The calculation results show the limitation in the performances of simple cycles and suggest the opportunity to resort to complex (binary) cycle configurations to achieve high net conversion efficiencies (15–16%).