Polarization switching in lead-free (K0.40Na0.60)NbO3 (KNN) single crystals was studied by switching spectroscopy piezoresponse force microscopy (SS-PFM). Acquisition of multiple hysteresis loops on a closely spaced square grid enables polarization switching parameters to be mapped in real space. Piezoresponse amplitude and phase hysteresis loops show collective symmetric/asymmetric characteristics, affording information regarding the switching behavior of different domains. As such, the out-of-plane polarization states of the domains, including amplitudes and phases can be determined. Our results could contribute to a further understanding of the relationships between polarization switching and polarization vectors at the nanoscale, and provide a feasible method to correlate the polarization hysteresis loops in a domain under an electric field with the polarization vector states.