Vibrational and rotational temperatures were simultaneously determined in a kilohertz alternating current (ac) gliding arc discharge by using overlapped emission spectra of N2(C 3Πu–B 3Πg) with OH(A 2Σ+–X 2Πi) and with . The simulated emission spectra of OH(A 2Σ+–X 2Πi) and were largely overlapped by radiation transition bands of N2(C 3Πu–B 3Πg) when the rotational temperature was elevated from 500 K to 2500 K. The temporally resolved vibrational and rotational temperatures in a discharge voltage period suggested that the rotational temperature from OH(A 2Σ+–X 2Πi) was remarkably larger than that from N2(C 3Πu–B 3Πg) and . The ratio of number densities of excited electronic states was also determined based on the overlapped emission spectra.