Transonic flows of a molecularly complex organic fluid through a stator cascade were investigated by means of large eddy simulations (LESs). The selected configuration was considered as representative of the high-pressure stages of high-temperature Organic Rankine Cycle (ORC) axial turbines, which may exhibit significant non-ideal gas effects. A heavy fluorocarbon, perhydrophenanthrene (PP11), was selected as the working fluid to exacerbate deviations from the ideal flow behavior. The LESs were carried out at various operating conditions (pressure ratio and total conditions at inlet), and their influence on compressibility and viscous effects is discussed. The complex thermodynamic behavior of the fluid generates highly non-ideal shock systems at the blade trailing edge. These are shown to undergo complex interactions with the transitional viscous boundary layers and wakes, with an impact on the loss mechanisms and predicted loss coefficients compared to lower-fidelity models relying on the Reynolds-averaged Navier–Stokes (RANS) equations.