The assessment of cucurbituril (CBn) for selective removal of actinides from nuclear waste streams requires comprehensive understanding of binding parameters and coordination of these complexes. The present work is the first experimental report on complexation of actinide ion with Cucurbituril (CB5) in solution. The thermodynamic parameters (ΔG, ΔH and ΔS) for complexation of CB5 with U(VI) in formic acid water medium were determined using microcalorimetry and UV-Vis spectroscopy. The enthalpy and entropy of complexation revealed the partial binding of U(VI) to CB5 portal. The partial binding was confirmed by spectroscopic techniques viz. extended X absorption fine structure spectroscopy (EXAFS), 1H and 13C NMR. The EXAFS χ(r) versus r spectra for U-CB5 complex has been fitted from 1.4 to 3.5 Å with two oxygen shells and a carbon shell. The presence of three carbon atom in secondary shell shows the involvement of only three carbonyl oxygens directly bonding to U(VI) which is in contrast to that calculated from gas phase DFT calculation of unhydrated system. The combined effect of hydration and formic acid encapsulation led to the enhanced stability of partially bound U(VI) to CB5. In the present work the binding of formic acid has also been studied by fluorescence spectroscopy. ESI-MS data shows the unusual stabilization of U(VI) by CB5 in gas phase.