This study reports on the first monodispersed molecular materials embodying the dibenzothiophene-5,5-dioxide core for the achievement of blue electroluminescence. The core has been functionalised in its 2,8- or 3,7-positions with dimethyl-fluorene (2,8-DBTOF and 3,7-DBTOF) or methyl-carbazole (2,8-DBTOC and 3,7-DBTOC) groups. The obtained compounds were characterised by 1H and 13C NMR, APCI-MS, thermal analysis (TGA and DSC) and cyclic voltammetry. Their optical and photophysical properties were investigated by UV and PL measurements as well as by time-dependent density-functional theory calculations. The materials were successfully employed as active layers in blue to purplish blue p-i-n OLED devices, that reached, in the case of 3,7-DBTOC, performances as high as 11 422 cd m−2 and 3.25 cd A−1.