This paper presents a new family of pyrimidine-based BF2 complexes. The series contains six examples of 1,1-difluoro-3-aryl(heteroaryl)-1H-pyrimido[1,2-c][1,3,5,2]oxadiazaborinin-9-ium-1-uides (2) — in which aryl(heteroaryl) = phenyl, 4-MeC6H4, 4-N(CH3)2C6H4, 4-NO2C6H4, 2-naphthyl, and 2-thienyl. The heterocycles 2 were easily synthesized at yields of 50–68% from reactions — at room temperature for 24 h — of simple N-(pyrimidin-2-yl)benzamides (1) with BF3·Et2O, and they were fully characterized by 1H-, 13C-, 19F, 11B-NMR, GC–MS, and X-ray diffractometry. Moreover, the photophysical properties, TD-DFT analysis, BSA-binding experiments, and molecular docking studies for the new organoboron complexes 2 were determined, presented, discussed, and compared with similar compounds that have already been described.