The development of Ïâconjugated molecular systems with highâefficiency generation of UV and blue light plays an important role in the fields of lightâemitting diodes, fluorescent imaging, and information storage. Herein, supramolecular construction of solidâstate UV/blue luminescent materials are assembled using 2,5âdiphenyloxazole (DPO) with four typical coâassembled building blocks (1,4âdiiodotetrafluorobenzene, 4âbromotetrafluorobenzene carboxylic acid, pentafluorophenol, and octafluoronaphthalene). Compared with the pristine DPO sample, the asâprepared twoâcomponent molecular materials feature ease of crystallization, high crystallinity, enhanced thermal stability and tunable luminescence properties (such as emissive wavelength, color, fluorescence lifetime, and photoluminescence quantum yield) as well as multicolor polarized emission in the UV/blue region. Moreover, pumpâenhanced luminescence and reversible mechanochromic fluorescence (MCF) properties can also be obtained for these molecular solids, which are absent for the pristine DPO sample. Therefore, this work provides a procedure for the facile selfâassembly of ordered twoâcomponent molecular materials with tunable UV/blue luminescence properties, which have potential application in the areas of lightâemitting displays, polarized emission, frequency doubling, and luminescent sensors.