A series of 1,3-bis(perfluoroaryl)-2-(hetero)aryl-1,3,2-benzodiazaboroles, 1,3-(F)Ar2-2-Ar-1,3,2-N2BC6H4 (Ar = Ph, (F)Ar = C6F5; Ar = Ph, (F)Ar = 4-C5F4N ; Ar = Ph, (F)Ar = 4-NCC6F4; Ar = 2-C4H3S, (F)Ar = C6F5; Ar = 2-C4H3S, (F)Ar = 4-C5F4N ; Ar = 2-C4H3S, (F)Ar = 4-NCC6F4), were synthesised by cyclocondensation of the adducts PhBBr2·PPh3 or 2-thienylBBr2·PPh3 with N,N'-bis(perfluoroaryl)-o-phenylenediamines in the presence of 2,2,6,6-tetramethylpiperidine. Similar treatments of the PPh3 adducts of 4-(1',3'-diethyl-1',3',2'-benzodiazaborolyl)-phenyldibromoborane with the corresponding diamines gave rise to the push-pull compounds, C6H4(NEt)2B-1,4-C6H4-B(N(F)Ar)2C6H4 ((F)Ar = C6F5; 4-C5F4N ) and C6H4(NEt)2B-2,5-C4H2S-B(N(F)Ar)2C6H4 ((F)Ar = C6F5; 4-C5F4N ). The X-ray structures of , , and were determined. Electronic structure calculations reveal that the LUMOs are located at the perfluoroaryl groups in ; thus the fluorinated benzodiazaborolyl groups are considered as electron-withdrawing moieties. These moieties differ from alkylated benzodiazaborolyl groups which are regarded as donors. The emission spectra for show charge transfer bands with significant solvatochromism and large Stokes shifts (6100-12 500 cm(-1) in cyclohexane and 8900-15 900 cm(-1) in CH2Cl2). The emissions of the benzodiazaboroles, , arise from a different charge transfer (CT) process to the local charge transfer (LCT) process typically found in many fluorescent benzodiazaboroles. This novel remote charge transfer (RCT) process involving the perfluoroaryl groups is supported by CAM-B3LYP computations. The push-pull systems here give fluorescent emissions with moderate to high fluorescence quantum yields (65-97%) that arise from the usual LCT process only.