This work was inspired by a previous report [Janjua, M.R.S.A. Inorg. Chem. 2012, 51, 11306−11314] in which the nonlinear optical (NLO) response strikingly improved with double heteroaromatic rings. Herein, series of triphenylamine–dicyanovinylene based donor−π–acceptor dyes had been designed by structural tailoring of π-conjugated linkers and theoretical descriptions of their molecular NLO properties were reported. Density functional theory and time-dependent density functional theory calculations were performed on optimized geometries to elucidate the electronic structures, absorption spectra, and NLO properties and also to shed light on how structural modification influences the NLO properties. The simulated absorption spectra results indicate that all of the dyes showed the maximum absorbance wavelength in the visible region. The lowest unoccupied molecular orbital–highest occupied molecular orbital energy gaps of all of the dyes have been found smaller, which results in large NLO response. Calculation...