A novel surface spectroscopic method referred to itself as noncontact atomic force spectroscopy (nc-AFS) is presented, which is based on noncontact atomic force microscopy (nc-AFM) and scanning tunneling spectroscopy (STS) of the family of scanning probe microscopy (SPM). The interaction force and current are measured with sweeping bias voltage between a tip and a sample at a close tip-sample separation, and analyzed in terms of surface spectroscopy. The spectra obtained by the nc-AFS indicate that the resonance states, i. e., covalent bonding, between a Si tip and a Si sample can be formed by tuning the bias voltage, corresponding to the relative shift of energy levels of tip states and sample states. Moreover, the nc-AFS combined with current measurement exhibits potential of evaluating the collapse of tunneling barrier and analyzing the correlation between force interaction and electron conductance between two pieces of condensed matter in proximity.