Designed, synthesized and characterized here two thiophene dyes 3-(4-(diethylamino)phenyl)-2-(thiophen-2-yl)acrylonitrile (ET), 3-(4-(diphenylamino)phenyl)-2-(thiophen-2-yl)acrylonitrile (PT) along with their -CHO substituted derivatives 3-(4-(diethylamino)phenyl)-2-(5-formylthiophen-2-yl)acrylonitrile (ET-CHO) and 3-(4-((4-formylphenyl) (phenyl)amino)phenyl)-2-(5-formylthiophen-2-yl)acrylonitrile (PT-2CHO) for optoelectronic devices towards protecting human eyes and optical sensors, as well as for stabilizing light sources in optical communications. Using the open aperture Z-scan method in tandem with linear absorption spectroscopy, emission spectroscopy and density functional theory (DFT) calculations, the nonlinear absorption and optical limiting behavior under nanosecond (5 ns) Nd: YAG laser excitation at 532 nm wavelength was demonstrated. The observed nonlinearity in all the samples was found to be arising from two-photon absorption process. The DFT calculations at a B3LYP/6-31G(d) level for the geometry optimization have shown that the HOMO levels of ET and PT dyes are delocalized throughout the molecule, while for ET-CHO and PT-2CHO dyes, they occupy all over the molecule except -CHO group present on thiophene ring. Also, LUMO levels are delocalized through the aromatic bridge and shift towards thiophene ring for all dyes. This change in the band structure has tuned the effective nonlinear absorption coefficients (βeff) and PT-CHO possesses a maximum value of βeff = 2.9 × 10−11 m/W. The excellent optical limiting performance of these chromophores makes them useful in photonic or optoelectronic devices for protecting human eyes and optical sensors, as well as for stabilizing light sources in optical communications.