The alignment and orientation of the excited electron cloud of the Li(3²D) state created at impact parameters between 0.2 and 1.1 au in 2.5-15 keV Li⁺-He charge-exchange collisions have been studied by means of Stokes parameter analysis of the photons emitted in the subsequent 3²D to 2²P transition. The experimentally determined coherence parameters are qualitatively in good agreement with calculated parameters, even in scattering regions where two-electron processes could be expected to contribute to the creation of Li(3²D). The calculated parameters are obtained by means of the molecular-orbital expansion method, taking molecular translations factors into account. The quantitative discrepancies are attributed to limitations in the calculations since two-electron processes and interactions between the Li(3²D) state and higher-lying states are neglected.