Five halogen-free (HF) dummy plastic ball grid array (PBGA) components with daisy-chains and Sn4.0Ag0.5Cu (SAC405) Pb-free solder balls were assembled on a HF high density interconnection (HDI) printed circuit board (PCB) using Sn1.0Ag0.5Cu (SAC105) and Sn3.0Ag0.5Cu (SAC305) Pb-free solder pastes, respectively. The above compositions were in weight percent. The assemblies were then experienced to moisture sensitive level testing with three times reflow at a peak temperature of 260 °C; no delamination was found present in both the component and PCB laminates. The microstructure showed that the utilization of SAC105 solder paste was beneficial in refining the Ag3Sn intermetallic compound (IMC) within the solder joint and the intermetallic layers formed at various interfaces with different Ni contents and thicknesses due to different metal finishes. The IMC spalling was found at the BGA-side interface within the solder joints formed with SAC105 solder paste but not discovered within the ones made of SAC305 solder paste. The pull strength of the solder joint formed with SAC305 solder paste was always higher than that made from SAC105 no matter on Cu or electroless Ni. Moreover, the fracture was found at the interface between the Cu foil and epoxy in the halogen-free test device. Numerical analysis showed that the thickness of IMC layer dominated the pull strength of the solder joint because the Z-axial normal stress applied to the solder joints formed with Cu and electroless Ni were 752.0 and 816.6 MPa, respectively, and a thicker IMC layer was beneficial to provide a higher pull strength of solder joint.