A new polymorph of LaNbO4 with a BaMnF4-type structure (a = 0.3938(2) nm, b
= 1.442(1) nm, c = 0.5682(3) nm, Z = 4) and octahedral oxygen coordination
of Nb was prepared at high pressures and temperatures (8 GPa, 1570 K). At
normal pressure, the reverse transformation, from high-pressure LaNbO4 to t
he M-fergusonite form, occurs at temperatures above 870 K and is close to a
second-order phase transition. The spontaneous polarization in high-pressu
re LaNbO4, evaluated from the second-order nonlinear optical response, is a
bout 2 mu C/cm(2).