Multiphoton ionization of NO via intermediate Rydberg states with ultra-short laser pulses is investigated with time-resolved photoelectron spectroscopy in combination with fermosecond pump-probe technology. The Rydberg states of NO, which are characterized by obvious ac-Stark shift in ultra-strong laser field, can be tuned in resonance to ionize NO molecule at one's will with identical laser pulses, i.e., one can 'select' resonance path to ionization. The results shown in this Letter demonstrate that the states holding notable dynamic Stark shift provide us another dimension to chemical control with strong laser field. (C) 2003 Elsevier Science B.V. All rights reserved.