A method for determining a communication path of millimeter wave signal and measurement device using the method includes a first measuring device and a second measuring device. The first measurement device queries a list to determine a first AOD of the first measurement device corresponding to a LOS, and controls the array antenna of the first measurement device to send the millimeter wave signal at the first AOD of the first measurement device corresponding to the LOS to the second measurement device. The second measurement device queries the list to determine a first AOA of the second measurement device corresponding to the LOS, and controls the array antenna of the second measurement device to receive the millimeter wave signal at the first AOA of the first measurement device corresponding to the LOS. Thus, a downlink between the first measurement device and the second measurement device can be quickly established.