By using optical emission spectroscopy (OES), the vibrational and rotational temperatures of N(+2) and N2 in dual frequency (41/2 MHz) capacitively coupled plasma (CCP) discharges are investigated.The vibrational and rotational temperatures are measured based on the N2 first negative system and N2 second positive system overlapped molecular emission optical spectrum, using the method of comparing the measured and calculated spectra with a least-square procedure.