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