Symmetrically and unsymmetrically 2,5-difunctionalized phospholes bearing ester groups were prepared in a one-pot procedure from the corresponding diynes and dichloro(phenyl)phosphine via titanacyclopentadienes. The observed optical properties of the functionalized phospholes show that the pi-conjugative push-pull interaction between the 2- and 5-substituents plays an important role in controlling the light-emitting efficiency.