Accurate XAFS spectra of solid and liquid rhodium at very high temperature have been recorded at the European Synchrotron Radiation Facility. Experiments have been analysed using advanced data analysis techniques and the results are compared with molecular dynamics simulations performed using several different pair functionals as model potentials. High-temperature data provided new insight on the details of the interaction potential allowing us to test the validity of different functional forms. The short-range g(r) at about 2300 K of liquid Rh and of the Rh-C alloy near the eutectic composition are measured for the first time and compared with MD results.