We report on the crystal structure evolution and the physical properties of the complex perovskite Pb(Fe0.5Ti0.25W0.25)O-3. It presents a paraelectric to ferroelectric transition at T-C = 293 K, determined by permittivity measurements. The room-temperature neutron powder diffraction pattern (NPD) shows an admixture of the ferroelectric phase (34%, P4mm space group) and the paraelectric polymorph (66%, Pm (3) over barm space group). In both polymorphs, the perovskite crystal structure contains the three B cations (Fe, Ti, W) distributed at random at the octahedral sites, and Pb is shifted away from the center of the cubic (sub)cell. On the other hand, the presence of iron drives the appearance of magnetic interactions above room temperature. This is related to the existence of Fe-rich islands where the strong Fe3+-O-Fe3+ superexchange interactions govern the magnetic behavior. The magnetic structure has been determined from low-temperature NPD experiments as a G-type antiferromagnetic (AFM) cell. Furthermore, there is a net magnetization in the entire range of temperature, which is related to the existence of noncompensated spins in each island. The coexistence of ferroelectricity and a magnetically ordered state and the observation of a possible coupling between both phenomena allow us to suggest the multiferroic-magnetoelectric nature of the sample.