The structures of mixed RbxCs2−xZnCl4 (x=0, 1, and 2) single crystals grown by using the slow evaporation method were determined with x-ray diffraction. In addition, the NMR spectra and the spin-lattice relaxation times, T1, of the R87b and C133s nuclei of the three crystals were determined by using nuclear magnetic resonance (NMR) spectroscopy. The spin-lattice relaxation times, T1, of the Cs-based compounds are very much longer than those of the Rb-based compounds. The differences between the T1 values of the Rb and Cs nuclei are due to the difference between their electric quadrupole moments. Further, we analyzed the crystallographic structures of these crystals by considering the occupation probabilities (Rb or Cs) of the two cationic sites. Our NMR experimental results confirm that there are two crystallographically inequivalent Rb sites, Rb(1) and Rb(2), in Rb2ZnCl4 and two crystallographically inequivalent Cs sites, Cs(1) and Cs(2), in Cs2ZnCl4. And, only one Rb site and only one Cs site in RbCsZnCl4 was obtained. The Cs and Rb occupation rates of each of the two available sites, A1 and A2, were determined from the NMR signals.