The new chromophore molecules with nonlinear optical (NLO) properties were prepared by Knoevenagel condensation from diformyl calix[4]arene and isophorone derivatives in the presence of piperidine and acetic acid, respectively. In these chromophore calix[4]arenes, the ring-locked trienes were employed as the conjugation bridge and electron acceptor in D-'pi'-A units. Nuclear magnetic resonance (NMR) spectra indicate that the non-conjugated D-'pi'-A units can be oriented at nearly the same direction. Hyper-Rayleigh Scatting (HRS) measurements and ultraviolet (UV) spectra indicate that they have higher first hyperpolarizability 'beta' values than the corresponding reference compounds and are not accompanied with a large shift (>25 nm) of the absorption band to longer wavelengths.