The double-well structure emerges as a result of the potential coupling in a molecular system. In this paper, taking the ionization of NO as an example, its influence on time-resolved photoelectron spectrum is investigated, by using the time-dependent wave packet method. The results reveal that the double-well structure formed by the crossing of NO excited state potentials supports several degenerate energy levels, which plays a crucial role in determining the dynamical behavior of NO molecule. It is also demonstrated that by adjusting the delay time of pump and probe laser pulses in the process of NO multiphoton ionization, the influence of double-well structure on time-resolved photoelectron spectrum can be manifested by the variation of vibrational population in the doublewell. The investigation about the effect of double-well structure on time-resolved photoelectron spectrum can provide us with a better understanding of dynamical behavior of molecules in external fields.