Redox interaction of reduced technetium forms and technetium(VII) with neptunium(III), neptunium(IV) and neptunium(VI) have been investigated using electrochemical and spectroscopic (Vis-NIR) techniques. The neptunium species most stable in 4 M H2SO4, i.e. Np(IV) ions, do not reduce Tc(VII) in contrast to Np(VI) ions which oxidize Tc(IV) species to Tc(VII). The interaction of pertechnetates with Np(III) leads to formation of Tc(IV) species. The Vis-NIR measurements showed the generation of intermediate Tc(V) and Np(V) forms during the oxidation of Tc(IV) and competitive reduction of Np(VI). Tc(V) and Np(V) forms are characterised by the bands at 460 and 980 nm respectively.