New dicyanovinyl-substituted 1-(alkyl)aryl-2-(2'-thienyl)pyrroles 2 were synthesized and characterized. The solvatochromic behavior of thesynthesized compounds was investigated. All the derivatives showed reversible oxidation and reduction on the CV time scale. Thehyperpolarizabilities () of compounds 2 were measured using hyper-Rayleigh scattering. The results are among the highest values reportedfor donor-acceptor-substituted thienylpyrroles.