We report on high-temperature crystallographic structure, magnetic and physical properties of chemically B-site disordered leadbismuth iron tungstate, (PFW) 1−x (BFO) x (which can be written as Pb 0.8 Bi 0.2 Fe 0.728 W 0.264 O 3 (0.8PFW-0.2BFO) for x = 0.2 and Pb 0.7 Bi 0.3 Fe 0.762 W 0.231 O 3 (0.7PFW-0.3BFO) for x = 0.3) or PBFW), solid solutions through neutron diffraction (ND), magnetization, electron paramagnetic resonance, and Mössbauer spectroscopic studies. From the high temperature magnetic susceptibility measurement, it is observed that increase antiferromagnetic to paramagnetic phase transition around T N = 435 K (Pb 0.8 Bi 0.2 Fe 0.728 W 0.264 O 3 ) and 504 K (Pb 0.7 Bi 0.3 Fe 0.762 W 0.231 O 3 ), compared to pure PFW. Room-temperature crystallographic study confirms the formation of pseudo cubic structure with Pm-3m space group, whereas the magnetic structure is commensurate G-type antiferromagnetic ordering. The obtained temperature dependent structural parameters from the ND, evidenced to existence of strong spin-lattice coupling around T N for both the compounds. The discontinuity in the Pb/Bi-O bond length around ferroelectric transition (T C ) indicates the presence of magnetoelectric coupling. Interestingly, microscopic 1:1 B-site ordered nanoclusters of PBFW exhibits the ferrimagnetic clusters along with antiferromagnetic order and it observed through the opening of M vs H hysteresis curves in the lower field regime. The EPR and Mössbauer spectroscopic studies well support the magnetic property and also reveal the Fe +3 state, and the weak signal in EPR and broader linewidth in the Mössbauer spectra exhibit the Bsite disorderliness.