The effects of 0 to 10 mol% excess-MgO addition on Pb(Mg1/2W1/2)O-3-PbTiO3 (PMW-PT) solid solutions were discussed. Excess-MgO addition successively changed the ferroelectric properties of PMW-PT. The material showed relaxer-type behavior with excess-MgO addition, whereas stoichiometric composition showed normal-ferroelectric-like properties, and further addition of 10 mol% caused dual peaks in the temperature dependence of the dielectric constant. These dual peaks were found to be attributed to aging phenomena. The excess MgO improved the degree of B-site ordering and local electric field based on defects, and it was suggested that the B-site ordering and the local field were responsible for the relaxer property and the aging effect, respectively.