Increasing our basic chemical knowledge of the actinyl cations ({AnO2}2+/+, where An = U, Np, Pu or Am) is vital for underpinning the development of novel nuclear waste management and nuclear fuel processing technologies, as well as increasing our understanding of actinide behaviour in the environment. Over recent years there have been significant advances made in uranyl, neptunyl and plutonyl chemistry, with the main focus on uranyl. At the Centre for Radiochemistry Research (CRR), University of Manchester, there are ongoing projects investigating the coordination chemistry of the actinyl cations. These projects are undertaken at the CRR and at higher specific activity alpha facilities accessed through Nexia Solutions and the EU ACTINET programme, as well as concomitant computational chemistry projects at University College London. Recent discoveries have included the complexation of transuranic actinyl cations with tri-lacunary heteropolytungstate ligands and spectroscopic and structural evidence for the direct coordination of the pertechnetate anion to {UO2}2+.