Phosphole-containing pi-systems have emerged as building blocks with enormous potential as electronic materials because of the tunability of the phosphorus center. Among these, asymmetric P-bridged trans-stilbenes are still rare, and here an elegant and efficient synthesis toward such fluorescent molecular frameworks is described. Fine-tuning of the photophysical properties is attempted by enforcing the planarization of the phosphorus tripod and thus increasing the interaction between the phosphorus lone pair and the pi-system, The electronic structure of the pi-conjugated frameworks is analyzed with NMR, UV-vis and fluorescence spectroscopy, and time-dependent density functional theory (TD-DFT) calculations.