Abstract A series of p -nitro substituted trans -diphenylbutadienes is synthesized and their photophysical and photochemical properties are investigated. All the dienes have a very low quantum yield of fluorescence but exhibit remarkable solvatochromic emission shifts attributed to twisted intramolecular charge transfer. Photochemical irradiation of simple p -nitro substituted diphenylbutadienes reveals inefficient or no detectable photoisomerization. However, substituting a methyl group on the butadiene chain of p -nitro substituted diphenylbutadiene or replacing the nitro group with cyano group yields the corresponding trans – cis isomers. In the case of simple nitrodienes, strong intramolecular charge transfer character in the excited state aids dissipation of absorbed energy through non-photochemical and non-radiative channels. The steric effect caused by the presence of methyl group lowers the isomerization barrier in methyl substituted dienes leading to a regioselective isomerization.