The isotopic phonon effects in LaB(6) are investigated on the Raman spectra of a series of high-quality single crystals with systematically varied contents of (10)B and (11)B isotopes. A detailed group theoretical analysis enlightens the correlation between distortions of the B(6) octahedra and the splitting or broadening of phonon modes. It is evident that LaB(6) does not have cubic symmetry as assumed so far. A further symmetry reduction of the B(6) octahedra occurs in isotopically mixed crystals. There, the distribution of isotopes is not random as commonly assumed; the probability of associating equal isotopes increases with their mass decreasing.