It is highly urgent to develop synthetic strategies to make new category of stable luminescent radicals with desired emission wavelength. In this study, we have isolated two dioxoborocyclic radicals ( 3 and 4 ) by a direct sy nthetic rou te. They were charac terized by UV, EPR spectroscopy and SQUID measurements. Their structures were obtained by single crystal X ray diffraction. Both radicals produce blue photoluminescence (458 nm for 3 and 478 nm for 4 ) by radiative decay from higher excited states (D2/D3) to the ground state (D0) based on theoretical calculation, breaking Kasha rule. The work records a new kind of radical emitters and the first stable radicals with blue emission bands.