<p>This work investigates atomic-scale partial B-site ordering in the complex perovskite relaxor lead iron tungstate, Pb[Fe_1−x​W_x​]_0.5​[Fe_1/3+x​W_2/3−x​]_0.5​O₃ (0 &lt; x &lt; 1/3), abbreviated as PFWO, using Time Differential Perturbed Angular Correlation (TDPAC) spectroscopy. The radioactive isotope ^111mCd (decaying to ¹¹¹Cd) is employed as a sensitive tracer probe to explore the local electric and magnetic environments at atomic sites within the lattice. Temperature-dependent TDPAC measurements performed over a broad range (9–420&#xa0;K) reveal the persistence of local electric field gradients at the Pb²⁺ sublattice in the face-centered cubic (<i>Fm-3&#xa0;m</i>) structure. This observation indicates local symmetry breaking due to partial B-site ordering, wherein Fe³⁺ and W⁶⁺ ions exhibit a degree of site preference, and confirms the presence of short-range polar ordering characteristic of relaxor ferroelectric behavior. Moreover, the detection of a non-zero local magnetic field at the Pb site—where complete spin compensation would be expected in an ideal antiferromagnetic configuration—provides compelling evidence for ferrimagnetic ordering. This ferrimagnetism is attributed to partial B-site cation ordering, resulting in unequal sublattice magnetizations and incomplete spin cancellation. These findings highlight the critical role of atomic-scale B-site ordering in mediating the coexistence of relaxor ferroelectricity and ferrimagnetism in PFWO.</p>