The use of Surface Plasmon Resonance as a powerful tool for the nonlinear c
haracterization of ultrathin dielectric layers is proposed and experimental
ly demonstrated. The off-resonant chi ((3)) of thin films (10-50 nm) of the
soluble polycarbazolyldiacetylene PDCHD-HS deposited on silver was measure
d at 1064 nm and with picosecond pulses: all samples exhibited a negative a
nd real chi ((3)) of the order of 10(-17) m(2)/V-2.