For many years, organoboron compounds have been expected to show excellent electron-injecting and -transporting properties. However, lowest unoccupied molecular orbital (LUMO) energy levels (E-LUMO) of B-containing pi-conjugated molecules are mostly higher than -4.0 eV and their electron mobilities are usually less than 10(-2) cm(2) V-1 s(-1). In this work, we experimentally prove the remarkably high electron affinity and high electron mobility of organoboron compounds. Our strategy is to incorporate multiple boron-nitrogen coordination bonds (B <- N) into azaacenes. We synthesized quadruply B <- N-fused dibenzo-azaacene (QBNA) through one- pot multifold borylation cyclization reaction. The incorporation of four B <- N units greatly changes the electronic structures and properties and significantly downshifts the electronic energy levels of QBNA. QBNA shows a E-LUMO of as low as -4.58 eV, which is among the lowest for n-type organic semiconductors. Single-crystal organic field-effect transistors of QBNA display unipolar n-type characteristic with an electron mobility of up to 1.60 cm(2) V-1 s(-1) together with excellent ambient stability. This study thus provides a design strategy for high-performance n-type organic semiconductors and high electron-affinity Jr-systems based on organoboron chemistry.