The formation of excitons in organic molecules by charge injection is an essential process in organic light-emitting diodes (OLEDs)1,2,3,4,5,6,7. According to a simple model based on spin statistics, the injected charges form spin-singlet (S 1 ) excitons and spin-triplet (T 1 ) excitons in a 1:3 ratio2,3,4. After the first report of a highly efficient OLED2 based on phosphorescence, which is produced by the decay of T 1 excitons, more effective use of these excitons has been the primary strategy for increasing the energy efficiency of OLEDs. Another route to improving OLED energy efficiency is reduction of the operating voltage2,3,4,5,6. Because T 1 excitons have lower energy than S 1 excitons (owing to the exchange interaction), use of the energy difference could—in principle—enable exclusive production of T 1 excitons at low OLED operating voltages. However, a way to achieve such selective and direct formation of these excitons has not yet been established. Here we report a single-molecule investigation of electroluminescence using a scanning tunnelling microscope8,9,10,11,12,13,14,15,16,17,18,19,20 and demonstrate a simple method of selective formation of T 1 excitons that utilizes a charged molecule. A 3,4,9,10-perylenetetracarboxylicdianhydride (PTCDA) molecule21,22,23,24,25 adsorbed on a three-monolayer NaCl film atop Ag(111) shows both phosphorescence and fluorescence signals at high applied voltage. In contrast, only phosphorescence occurs at low applied voltage, indicating selective formation of T 1 excitons without creating their S 1 counterparts. The bias voltage dependence of the phosphorescence, combined with differential conductance measurements, reveals that spin-selective electron removal from a negatively charged PTCDA molecule is the dominant formation mechanism of T 1 excitons in this system, which can be explained by considering the exchange interaction in the charged molecule. Our findings show that the electron transport process accompanying exciton formation can be controlled by manipulating an electron spin inside a molecule. We anticipate that designing a device taking into account the exchange interaction could realize an OLED with a lower operating voltage.