Nafion or sodium poly(styrenesulfonate) (NaPSS) entrapped in either sol-gel-derived silica or cross-linked poly(vinyl alcohol) (PVA) composite coatings on spectroscopic graphite electrodes were investigated electrochemically with [Re I (DMPE) 3 ] + , where DMPE ) 1,2-bis-(dimethylphosphino)ethane. Among these composite coatings, Nafion-entrapped sol-gel-derived silica (Nafionsilica) exhibited a sensitivity for [Re I (DMPE) 3 ] + ∼4 times higher than that of NaPSS-entrapped sol-gel-derived silica or NaPSS-entrapped PVA. When Nafion was entrapped in cross-linked PVA matrix, however, the voltammetric response was found to be only ∼14% of that of Nafion and Nafion-silica composite coatings. Dispersing Nafion in sol-gel-derived silica matrix improves the slow diffusion of [Re I (DMPE) 3 ] + in Nafion, thus leading to a higher sensitivity than Nafion in a shorter preconcentration time. Such a Nafion-silica composite is promising for both electrochemical and spectroelectrochemical sensing of [Re I (DMPE) 3 ] + . It was also found that increasing the high potential of a cyclic voltammetric scan greatly reduces the amount of [Re II (DMPE) 3 ] 2+ available for reduction in the reverse potential scan, suggesting that the electrochemically generated [Re II (DMPE) 3 ] 2+ was consumed in the more positive potential region.[Re I (DMPE) 3 ] + , where DMPE ) 1,2-bis(dimethylphosphino)-ethane, is a nonradioactive analogue of [ 99m Tc I (DMPE) 3 ] + , which is radioactive and shows potential as a myocardial perfusion imaging agent. 1 Radiopharmaceuticals are routinely used for organ imaging and for radiotherapy in nuclear medicine. One of the fundamental problems associated with the use of radiopharmaceuticals is that, in many circumstances, the composition of an injected radiopharmaceutical is known, but the chemical form of the agent that is actually responsible for the imaging or therapy may be an altered form due to in vivo reactions. 2 This is evidenced by biological studies which show that in vivo redox reactions can markedly affect the biodistributions of technetium-99m and rhenium-186 radiopharmaceuticals. 3,4 Therefore, gaining the information regarding the chemical form that is responsible for imaging or therapy is crucial for developing more efficacious radiopharmaceuticals. By investigating the nonradioactive species, [Re I (DMPE) 3 ] + , information directly applicable to its radioactive analogue can be acquired and information related to other radiopharmaceuticals may also be extracted.We have recently shown the preferential uptake of [Re I -(DMPE) 3 ] + by Nafion, a perfluorosulfonated ionomer, and the potential utility of Nafion as an electrode modifier to enhance electrochemical detection of [Re I (DMPE) 3 ] + . 5,6 [Re I (DMPE) 3 ] + ion strongly partitions into Nafion films, 5 due to the electrostatic interaction and, to some extent, hydrophobic interaction of Nafion ionomer with the hydrophobic cation. However, we have found the partitioning process for [Re I (DMPE) 3 ] + into Nafion films to be slow. 5,6 A slow...