The single-phase Bi1-xNdxFeO3 (x=0, 0.05, 0.10, 0.15, 0.20) were synthesized by the sol-gel method. Their crystal structure and microwave electromagnetic property in the frequency range of 2–18GHz were investigated. The XRD patterns and Raman spectra showed that structural transition from rhombohedral (x=0, 0.05, 0.1) to triclinic (x=0.15) and tetragonal structure (x=0.20) appeared in the Bi1-xNdxFeO3. Electromagnetic measurement suggested that both microwave permeability μ′ and magnetic loss tanδm increased remarkably over 2–18GHz by doping Nd. Strong dielectric loss peak was observed on the samples of Bi1-xNdxFeO3 (x=0.15) and Bi1-xNdxFeO3 (x=0.2). Results show that Nd substitution is an effective way to push BiFeO3 to become microwave absorbing materials with high performance.