Dipyrroles with a phenylene bridge, 1,4-bis(pyrrol-2-yl)benzene, 4-(1-vinylpyrrol-2-yl)-1-(pyrrol-2-yl)benzene, and 1,4-bis(1-vinylpyrrol-2-yl)benzene, show intense room-temperature fluorescence in solutions. Analysis of electronic absorption spectra, fluorescence spectra, and results of B3LYP, TD B3LYP, and CIS quantum chemical calculations showed that the introduction of a bulky substituent in position 1 of the pyrrole ring makes the ground-state structures of dipyrrolylbenzenes less planar. Excited-state geometries of all molecules relax to more planar conformations. An increase in the probability of nonradiative transitions has little effect on the quantum yields of fluorescence (Φf) of dipyrrolylbenzenes. Even for 1,4-bis(1-vinylpyrrol-2-yl)benzene, where the pyrrole rings deviate from the benzene ring plane by 44°, the fluorescence efficiency remains high enough (Φf = 0.7). Substitution at nitrogen atoms has little effect on positions of fluorescence band maxima.