In this paper, a novel impedance spectroscopy was used to describe the thermal behaviors of Ni-MH batteries. The impedance functions were derived similarly to electric impedance functions. The square of current was treated as a current equivalent and heat-flow as a voltage equivalent. The impedance spectra of batteries during charge showed that the combination of hydrogen and oxygen increased rapidly when charge rate was higher than 0.5C. Thermal runaway might happen when battery was charged at temperature above 348K even at a low charge rate. The cycling test showed that the charge efficiency of battery was the highest after cycling at high-rate for 10–100 cycles and decreased after more cycles. Different batteries showed different thermal behaviors which may be caused by the different structures of batteries.