Synchronization signals are requisite for calibrating electrical measurement devices with digital output when using conventional calibration methods. However, since the signal sampling process of the analogue merging units (MUs) operating in an intelligent substation does not rely on external synchronization signals, accuracy calibration without the use of synchronization signals is of particular importance in order to guarantee the measurement accuracy in practical situations. So far, very little research on calibration systems independent of synchronization signals has been performed. This paper presents a design of the calibration system without dependence on synchronization signals. To verify the feasibility of the proposed design, the designed system and a conventional calibration system have been employed in testing the accuracy of the same analogue MU of a 0.2 accuracy class. The comparison of the test results shows that the differences of ratio errors are below 0.02%, and the maximum difference of phase errors is about 4 ′ . This paper also provides a new efficient and significant calibration method which does not require any external synchronization signals.