A new family of p-quaterphenyls 1-6 laterally substituted with a bulky electron-accepting dimesitylboryl group has been designed and synthesized. These compounds were characterized by X-ray crystallography, UV-vis and fluorescence spectroscopy, and DFT calculations as well as thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and cyclic voltammetry (CV). X-ray single-crystal analysis revealed that the p-quaterphenyl main chain framework exhibits a twisted structure due to the steric effect of the lateral boryl group, and the intermolecular interactions are effectively suppressed in the solid state. Despite the significantly twisted main-chain structure, these molecules still display efficient intramolecular charge-transfer emissions with large Stokes shifts. An intriguing finding is that all these molecules show bright fluorescence with good to excellent quantum yields in the blue region in the solid state. In addition, the two representative p-quaterphenyls 3 and 4 containing both the electron-accepting boryl group and the electron-donating carbazolyl (3) or diphenylamino group (4) possess high thermal stability and good oxidation-reduction reversibility, which together with their excellent solid-state fluorescence efficiency make them promising bipolar transporting blue emitters.