The fission yield of 99Tc from 239Pu and 235U is similar to that of 137Cs or 90Sr and it is therefore an important component of nuclear weapons fall-out, nuclear waste and releases from nuclear facilities. There is particular current interest in 99Tc transfer from soil to plants for: (a) environmental impact assessments for terrestrial nuclear waste repositories, and (b) assessments of the potential for phytoextraction of radionuclides from contaminated effluent and soil. Vascular plants have a high 99Tc uptake capacity, a strong tendency to transport it to shoot material and accumulate it in vegetative rather than reproductive structures. The mechanisms that control 99Tc entry to plants have not been identified and there has been little discussion of the potential for phytoextraction of 99Tc contaminated effluents or soil. Here we review soil availability, plant uptake mechanisms and soil to plant transfer of 99Tc in the light of recent advances in soil science, plant molecular biology and phytoextraction technologies. We conclude that 99Tc might not be highly available in the long term from up to 50% of soils worldwide, and that no single mechanism that might be easily targeted by recombinant DNA technologies controls 99Tc uptake by plants. Overall, we suggest that Tc might be less available in terrestrial ecosystems than is often assumed but that nevertheless the potential of phytoextraction as a decontamination strategy is probably greater for 99Tc than for any other nuclide of radioecological interest.