The "devil's staircase"-type phase transition in the quarter-filled spin-la
dder compound NaV2O5 has been discovered at low temperature and high pressu
re by synchrotron radiation x-ray diffraction. A large number of transition
s are found to successively take place among higher-order commensurate phas
es with 2a x 2b x zc type superstructures. The observed temperature and pre
ssure dependence of modulation wave number q(c). defined by 1/z. is well re
produced by the axial next nearest neighbor Ising model. The q(c) is sugges
ted to reflect atomic displacements presumably coupled with charge ordering
in this system.