Organic light-emitting diodes (OLEDs) with thermally activated delayed fluorescence (TADF) materials have advantages such as high efficiency with low cost compared to OLEDs with conventional fluorescence and phosphorescence materials. To attain further high device performance, clarifying internal charge states in OLEDs at a microscopic viewpoint is crucial; however, only a few such studies have been performed. Here, we report a microscopic investigation into internal charge states in OLEDs with a TADF material by electron spin resonance (ESR) at a molecular level. We observed operando ESR signals of the OLEDs and identified their origins due to a hole-transport material PEDOT:PSS, gap states at an electron-injection layer, and a host material CBP in the light-emitting layer by performing density functional theory calculation and studying thin films used in the OLED. The ESR intensity varied with increasing applied bias before and after the light emission. We find leakage electrons in the OLED at a molecular level, which is suppressed by a further electron-blocking layer MoO3 between the PEDOT:PSS and light-emitting layer, resulting in the enhancement of luminance with a low-voltage drive. Such microscopic information and applying our method to other OLEDs will further improve the OLED performance from the microscopic viewpoint.