Palladium (Pd) coated copper (PCC) wire is an emerging bonding wire that has been widely researched. In this paper, the effects of electronic flame-off (EFO) current and EFO time on the free air ball (FAB) morphology of four PCC wires with Pd layer thicknesses of 60, 80, 100, and 120 nm, respectively, are first investigated. The larger the EFO current or the longer the EFO time, the larger the FAB diameter. The EFO time or EFO current setting is either too high or too low to form a FAB with good morphology. Taking the ratio of FAB diameter to wire diameter as 2 as the standard, the EFO current of 48 mA and the EFO time of 700 μs are selected as the optimal EFO parameter combination. Under this parameter combination, the symmetry, roundness, and surface smoothness of the FAB of the four PCC wires are all at a better level. It is found that the FAB surface Pd coverage of PCC wire with 120 nm Pd layer thickness is higher through the corrosion test. The Pd transfer law on the FAB at different EFO times under optimal EFO current is also studied. The results show that with the prolongation of the EFO time, the Pd on the FAB surface is gradually transferred from the neck to the middle and lower parts. This study can provide technical reference for the selection of Pd layer thickness and EFO parameters of PCC wire.