Spectroscopic, magnetochemical, and crystallographic data are presented for CsFe(H2O)(6)PO4, a member of a little-known isomorphous series of salts that facilitates the study of hexa-aqua ions in a quasicubic environment. Above 120 K, the deviations from cubic symmetry are minimal, as shown by the first example of an iron(II) Mossbauer spectrum that exhibits no measurable quadrupole splitting. Two crystallographically distinct [Fe(OH2)(6)](2+) complexes are identified from inelastic neutron-scattering (INS) experiments conducted between 2 and 15 K. The data are modeled with the ligand-field Hamiltonian, (H) over cap = lambda(L) over cap(S) over cap + beta B(k (L) over cap +2 (S) over cap)+Delta(tet){(L) over cap (2)(z)-(1/3)L(L+1)} + Delta(rhom) {(L) over cap (2)(x)-(L) over cap (2)(y)}, operating in the ground-term T-5(2g) (O-h) basis. An excellent reproduction of INS, Mossbauer, HF-EPR, and magnetochemical data are obtained in the 2 and 15 K temperature regimes with the following parameters: I) - 80 cm(-1); k = 0.8; site A Delta(tet) = 183 cm(-1), Delta(rhom) = 19 cm(-1); site B Delta(tet) = 181 cm(-1), Delta(rhom) = 12 cm(-1). The corresponding zero-field-splitting (ZFS) parameters of the conventional S = 2 spin Hamiltonian are as follows: site A D = 12.02 cm(-1), E = 2.123 cm(-1); site B D = 12.15 cm(-1), E = 1.37 cm(-1). A theoretical analysis of the variation of the energies of the low-lying states with respect to displacements along selected normal coordinates of the [Fe(OH2)(6)](2+), shows the zero-field splitting to be extremely sensitive to small structural perturbations of the complex. The expressions derived are discussed in the context of spin-Hamiltonian parameters reported for the [Fe(OH2)(6)](2+) cation in different crystalline environments.