Absolute rate coefficients for dielectronic recombination (DR) of Li-like 136 Xe 51+ have been measured at the heavy-ion storage ring ESR. The experimental results are compared with relativistic distorted-wave calculations employing the multiconfiguration Dirac-Fock method. Based on the DR measurements the 2 s -2 p 1/2 and 2 s -2 p 3/2 excitation energies in Li-like Xe 51+ were determined with a relative accuracy of ~400 ppm.