A series of second-order nonlinear optical (NLO) molecules, M1–M5, were designed and successfully synthesized through the convenient ‘‘click chemistry’’ reaction, which contain two different types of chromophore moieties, the FTC chromophore and nitro-based azo ones, according to the concept of “Isolation Chromophore”. All these five molecules possess excellent thermal stability and very large NLO performance, with an ultrahigh d₃₃ value of 384 pm V⁻¹ at the wavelength of 1950 nm achieved for M1, furthering the rational design of excellent NLO materials.