A novel method is reported whereby unconventional molecules without aliphatic tails may be noncentrosymmetrically aligned by the Langmuir-Blodgett technique, the molecules in this case having a central cationic acceptor and two pi-bridged donor groups with an angle of ca. 120degrees between the charge-transfer axes of the chevron-shaped D-pi-(A(+))-pi-D unit. Their LB films exhibit second-harmonic generation and molecular rectification.