A mode control apparatus of a hybrid vehicle is provided. The apparatus includes a first clutch that is disposed between an engine and a motor generating power and a second clutch that is disposed between the motor and a transmission. In addition, a controller is configured to execute engagement and disengagement of the first clutch and the second clutch. The controller is also configured to adjust the speed of the motor and the transmission to be synchronized by generating slip in the second clutch when a transition from an EV mode to an HEV mode is requested.