This paper reports on experiments aiming to understand and to characterize how the working fluid spreads in an organic Rankine cycle (ORC) power system. To this end, a 2-kWe ORC test rig is constructed and tested over a wide range of conditions. Besides standard thermo-hydraulic sensors, the fluid charge distribution is measured on-line by bending load cells and infrared imaging techniques. Following a complete experimental campaign (which includes more than 330 steady-state points and fully characterizes the ORC off-design behaviour), a dual data reconciliation method is applied to the raw measurements to obtain a reference dataset. The results are then analysed to assess the charge distribution mechanisms occurring in the ORC and how it is correlated with the system performance. Among other aspects, this paper demonstrates (i) how the charge inventory is highly correlated to the temperature profiles in the heat exchangers, (ii) how the evaporator dictates the operating conditions of the low-pressure components, and (iii) how the system charge and the liquid receiver size can be selected to maximize the ORC overall performance.