Discharge behaviors of high-power impulse magnetron sputtering with different targets have been investigated. Distinct current–voltage curves and target current waveforms are observed. Breakdown voltage and the maximum target current show a periodic drop with the increase of atomic number in subgroups and periods. The target current density is found to be mainly affected by the secondary electron emission yield. Thus, its magnitude is unable to directly evaluate the ionization degree of sputtered atoms in high-power impulse magnetron sputtering (HiPIMS) process. In this paper, the interactive influence of secondary electron emission, sputter yield, and ionization energy on the ionization degree of sputtered atoms is discussed based on the analysis of the voltage and current characteristics. As a result, targets can be categorized into three sorts according to the ionization degree: 1) low ionization degree targets, such as Ag and C less than 10%; 2) intermediate ionization degree targets like Cr and Cu with 55% and 35%; 3) Ti, Zr, and Mo targets with the second ionization processes. These results provide institutive operation ranges for the state-of-the-art HiPIMS applications.