The structural and dielectric properties of Pb(Mg1/3Nb2/3)O3 ceramics substituted by Nd3+, La3+, K+ and Na+ were studied over 0~50 at.% substituent content. The 1 : 1 ordering behavior of Mg2+ and Nb5+ ions in the B site sublattice was observed in Nd3+-and La3+-modified compounds. The degree of ordering was increased with Nd3+, La3+ content in the compounds. But K+-or Na+-modified compounds did not exhibit the ordering behavior. This was explained by charge and size effect of A and B site cations and oxygen vacancies. As the mole fractions of substituent increased, the maximum values of dielectric constants were rapidly decreased and the phase transitions were broadened. Phase transition temperature was correlated with the covalency of A-O and B-O bonding.