A novel procedure for the high-yield preparation of Re-188 radiopharmaceuticals containing a terminal Re identical with N multiple bond is described. This method involves the reaction of [(188)Re][ReO(4)](-) with N-methyl S-methyl dithiocarbazate (DTCZ), as donor of nitrido nitrogen atoms, sodium oxalate and SnCl(2) to afford a mixture of two intermediate compounds. When this mixture is reacted with the sodium salt of a dithiocarbamate ligand (L) of the type Na[R(2)N-C(=S)S] (R = CH(3), CH(3)CH(2), CH(3)CH(2)CH(2)), the formation of the bis-substituted, neutral complexes [(188)Re][Re(N)(L)(2)] is easily obtained in high yield (> 95%). The complexes [(188)Re][Re(N)(L)(2)] were characterized by chromatographic methods, and by comparison with the corresponding complexes prepared at macroscopic level starting from a non-radioactive rhenium precursor. Biodistribution studies were carried out in rats. Results showed that the complexes [(188)Re][Re(N)(L)(2)] exhibited the same biological behavior of the analogous Tc-99m complexes reported previously. The easy application of the new synthetic procedure indicates that it could be conveniently employed for preparing a large class of new Re-188 complexes having potential utilization in nuclear medicine as therapeutic agents.