The low temperature absorption and luminescence spectra of (PPh4)UOCl5 are reported. Changes in bond lengths in the first electronic excited state show that the highest filled molecular orbital contributes to bonds to the oxygen atom and to the trans chlorine atom, but not to the cis chlorines. This explains the shortness of the trans U-Cl bond compared with those in the cis positions, and provides an example of the phenomenon we have called the inverse trans influence.