We report the evidence of weak ferromagnetic and ferroelectric ordering in polycrystalline Pb(Fe0.634 W0.266Nb0.1)O3 (0.8(PbFe2/3W1/3)O3–0.2Pb(Fe1/2Nb1/2) O3) (PFWN) ceramic at room temperature. The Pb(Fe0.634 W0.266Nb0.1)O3solid solution synthesized through the columbite method. The obtained single-phase Pb(Fe0.634 W0.266Nb0.1)O3ceramic was subjected to X-ray diffraction, neutron diffraction, magnetization, Mössbauer spectroscopy, and ferroelectric measurements. The X-ray diffraction and neutron diffraction pattern confirms the formation of single phase without any traces of pyrochlore phases, having cubic structure with Pm-3m space group. The Rietveld refinements were carried out on both patterns, and ND data confirms the G-type antiferromagnetic structure with propagation vector (k = 1/2, 1/2, and 1/2). However, along with the antiferromagnetic ordering of the Fe spins, we also observed the existence of weak ferromagnetism. This result was confirmed through (i) a clear opening of hysteresis (M − H) loop, (ii) bifurcation of the field-cooled (FC) and zero-field-cooled (ZFC) susceptibilities, (iii) spin-glass behavior, and (iv) Mössbauer spectroscopy.