A novel nonlinear optical chromophore with rigid 3-bromo-thiophene (denoted as BTC) as a site-isolation group to suppress the dipole-dipole interaction, was designed and synthesized. UV–vis absorption indicated that BTC showed intensified absorption and large bathochromic solvatochromism. The electro-optic performance studies displayed a highest r33 value (93pm/V) at high chromophore loading density of 45%, which indicated that the dipole-dipole interactions were effectively suppressed. The Crystal analysis further demonstrated that the face-to-face antiparallel packing with a long distance of 7.388Ǻ between the neighboring chromophores was observed. This weak packing interactions suggested that BTC chromophores can be well isolated in electro-optic materials for chromophores’ high efficient alignment. The excellent electro-optic performances endowed BTC potential application in the high-performance electro-optic materials.