Fe-containing intermetallic compounds (IMCs) are among the most detrimental second phases in aluminum alloys. One particularly harmful type is θ-Al13Fe4, which exhibits a needle- or plate-like morphology, leading to greater degradation of mechanical properties compared to other Fe-IMCs with more compact structures, such as α-Al15(Fe,Mn)3Si2. The addition of alloying elements is a crucial strategy for modifying the microstructure during the solidification process of aluminum alloys. This study investigates the effects of adding vanadium (V) and zirconium (Zr) on the morphology and crystal chemistry of θ-Al13Fe4 in an Al-4Fe alloy, employing a combination of experimental observations, first-principle calculations, and thermodynamic analysis. Our findings indicate that zirconium significantly refines both the primary θ-Al13Fe4 particles and the α-Al grains. Additionally, a small amount of vanadium can be incorporated into one of the Wyckoff 4i Al sites in θ-Al13Fe4, rather than occupying any Fe sites, under casting conditions, in addition to the formation of binary Al-V phases.