The phase transformation of FeV (σ-phase) to Fe2VAl (L21-phase) has been studied by systematic variation of Al concentration in Fe2V2-xAlx (x = 0-1). Remarkable changes in magnetic properties were observed with different Al contents. Electrical transport and magnetic properties of these compositions have been investigated in the temperature range, which revealed that the disorder and impurity phase plays an important role in tuning the electronic properties. The observed magnetic anomalies above TC indicate the heterogeneous magnetic nature of these alloys. The role of Al in electronic transport and the correlation between structural, magnetic, and electrical transport properties are discussed. © 1965-2012 IEEE.