A Langmuir-Blodgett (LB) multilayer film of the unimolecular rectifier hexadecyl-gamma-quinolinium-7,7,8-tricyanoquinodimethanide (C16H33 gamma Q-3CNQ) has two distinct polarized charge-transfer bands, one at lower film pressures (28 mN m(-1)) with a peak at 530 nm, due to an intramolecular charge transfer or intervalence transfer (IVT); past the collapse point (32 to 35 mN m(-1)), this band disappears, and a new intermolecular charge-transfer band appears with peak at 570 nm. An LB multilayer film of the tetrafluoro analogue, hexadecyl-gamma-quinolinium-2,3,5,6-tetrafluoro-7,7,8-tricyanoquinodimet hanide (C16H33 gamma Q-3CNQF(4)) shows, for all film pressures, only one IVT band with a peak at 504 nm; when sandwiched between gold electrodes, (C16H33 gamma Q3CNQF(4) is also an LB monolayer electrical rectifier.