First ever measurements of the ratios of free cyclotron frequencies of heavy, highly charged ions with Z>50 with relative uncertainties close to 10^{-11} are presented. Such accurate measurements have become realistic due to the construction of the novel cryogenic multi-Penning-trap mass spectrometer PENTATRAP. Based on the measured frequency ratios, the mass differences of five pairs of stable xenon isotopes, ranging from ^{126}Xe to ^{134}Xe, have been determined. Moreover, the first direct measurement of an electron binding energy in a heavy highly charged ion, namely of the 37th atomic electron in xenon, with an uncertainty of a few eV is demonstrated. The obtained value agrees with the calculated one using two independent, different implementations of the multiconfiguration Dirac-Hartree-Fock method. PENTATRAP opens the door to future measurements of electron binding energies in highly charged heavy ions for more stringent tests of bound-state quantum electrodynamics in strong electromagnetic fields and for an investigation of the manifestation of light dark matter in isotopic chains of certain chemical elements.