In this study, (1-x)PbFe0.5Nb0.5O3(PFN)-(x)BiFeO3(BFO) multiferroic solid solutions with x=0.0, 0.1, 0.2, 0.3 and 0.4 were synthesized through single step solid state reaction method and characterized thoroughly through X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Fourier Transform Infra Red (FTIR), Raman, Mossbauer spectroscopy and ferroelectric studies. The room temperature (RT) XRD studies confirmed the formation of single phase with negligible amount of secondary phases (x=0.2 and 0.4). The zoomed XRD patterns of (1-x)PFN-(x)BFO solid solutions showed the clear structural phase transition from monoclinic (Cm) to rhombohedral (R3c) at x=0.4. The Raman spectra of the (1-x)PFN-(x)BFO solid solutions showed the composition dependent phase transition from monoclinic (Cm) to rhombohedral (R3c). With increasing x in PFN, the modes related monoclinic symmetry changes to those of rhombohedral symmetry. The RT Mossbauer spectroscopy results evidenced the existence of composition dependent phase transition from paramagnetic to weak antiferromagnetic ordering and weak antiferromagnetic to antiferromagnetic ordering. The Mossbauer spectroscopy showed paramagnetic behavior with a doublet for x=0.0, 0.1 and 0.2 are shows the weak antiferromagnetic with paramagnetic ordering. For x=0.3 and 0.4 shows the sextet pattern and it is a clear evidence of antiferromagnetism. The ferroelectric (P-E) loops at RT indicate the presence of small polarization, as the x concentration increases in PFN, the remnant polarization and coercive field were decreased, which may due to the increase in the conductivity and leaky behavior of the samples. (C) 2016 Elsevier B.V. All rights reserved.