Redox-labeled nucleotides are of increasing interest for next generation molecular tools and should meet requirements of being thermally stable, sensitive, and compatible with polymerase-mediated incorporation whilst also being electrochemically discriminable. We are reporting the labelling of deoxy and dideoxy nucleotides (dNTPs) and DNA primers for use in electrochemical array based primer extension for the detection of early dispositions for diseases. polyoxometalates (POMs), Organometalics, and organic molecules have been used to functionalize DNAs and investigate their potential use in diagnostics. POMs, which are inorganic metal oxido clusters, to DNA strands to obtain functional labeled DNA primers and their potential use in electrochemical detection have been investigated. Activated monooxoacylated polyoxotungstates [SiW₁₁O₃₉{Sn(CH₂)₂CO}]⁸⁻ and [P₂W₁₇O₆₁{Sn(CH₂)₂CO}]⁶⁻ have been used to link to a 5′-NH2 terminated 21-mer DNA forward primer through amide coupling. The functionalized primer was characterized by using a battery of techniques, including electrophoresis, mass spectrometry, as well as IR and Raman spectroscopy. The functionality of the POM-labeled primers was demonstrated through hybridization with a surface-immobilized probe. The labeled primers were successfully used in the polymerase chain reaction (PCR) and the PCR products were characterized by using electrophoresis.Inaddtion to this POM-deoxynucleotide (POM-dNTP) bioconjugates linked through 7 deaza modified purines is also studied. The modified POM-dNTPs were used for polymerase based amplification of a DNA sequence specific for Yersinia Pestis and the amplified DNA detected via an electrochemical DNA sensor. This highlights the potential of polyoxometalates as thermally stable, sensitive and polymerase-compatible redox labels for exploitation in bioanalytical applications.