Capacitance–voltage (C–V) characteristics of organic molecular semiconductors attracted much research interest recently, but no convincing physical mechanism has been established so far. In this work, the C–V characteristics of pentacene-based devices have been systematically investigated at various frequencies. Only one peak occurs when the measuring frequency is less than 3kHz or greater than 8kHz. While within the frequency range between the two, two C–V peaks are observed with quite different dependence on temperature, which suggests that the origins of these two C–V peaks are respectively mobile holes and trapped carriers. This conclusion is also experimentally validated with the C–V characteristics of intentionally doped devices.