A new class of cross-linkable N,N,N′,N′-tetraphenyl-1,1′- biphenyl-4,4′-diamine (TPD)-based hole-transporting materials (HTMs), DV-OMe-TPD, DV-Me-TPD, and DV-F-TPD, were designed and synthesized. Two vinyl groups in the TPD units are used for thermal cross-linking, whereas methoxy, methyl and fluoro groups are introduced to modulate the HOMO energy levels of the HTMs. These HTMs are thermally cross-linked to overcome interfacial mixing, realizing solution-processed polyfluorene (PFO)-based devices (ITO/cross-linked HTMs/PFO/CsF/Al). Besides the characteristic blue emission of PFO, the devices exhibited a red emission whose energy is highly dependent on the HOMO energy of the cross-linked HTM used in the device. This result suggests that the red electroluminescence is derived from the exciplex generated by the adjacent hole and electron at the cross-linked HTM/fluorenone heterojunction interface. By doping small amount of 4,7-bis(9,9-dihexylfluoren-2-yl)-2,1,3-benzothiadiazole (BFBT) into the emissive layer (EML) to compensate green emission, the devices with the configuration of ITO/PEDOT:PSS/DV-Me-TPD/PFO doped with BFBT/CsF/Al exhibited white electroluminescence comprising three primary colors simultaneously. The 0.04 wt % doped device achieved a maximum luminous efficiency of 5.28 cd/A, which represents the highest efficiency for WPLEDs reported so far on the basis of the exciplex strategy. This device showed CIE chromaticity coordinates of (0.32, 0.42) which are close to the ideal white point (0.33, 0.33). We have demonstrated that integrating cross-linked triarylamine-based HTMs with fluorenone defects in PFO to induce exciplex electroluminescence can provide a useful way for realizing WPLED devices.