I will strike that thought of a test account
a third MS Account on one PC might just confuse things
if you are able to extricate your wife's MS credentials and be able to issue her a new user profile – assuming that would not be a major disruption – that might help
what I am getting at is the problem may be related to some corruption in her user profile
btw do you see an entry for Microsoft SkyDrive/OneDrive in
Control Panel>Programs and Features?
ACTUALLY the easiest FIRST STEP would be to
switch her account to a local account
then the OneDrive sync app will not start up, and the OUC might get its bearings
(you can always switch back to MS Account later)
test a doc or two
reboot and see
FTR you have Windows 8.1 Home - NOT PRO?
ADD:
WHEN did this malfunction start?
did any thing happen around that time?
have you had any problems with SkyDrive/OneDrive itself?
are all updates applied?
**in File Explorer**in HER user profile
SkyDrive folder
are there any signs of problem files?
red - yellow? – messages?
in Modern app - top right corner>click
any file info?
and the SkyDrive folder is in its original location at
C:\Users\username\SkyDrive?
does everything look in OK at www.onedrive.com?
and there is only ONE installation of Microsoft Office in
Control Panel>Programs and Features?
are there any other strange things going on with the PC in either user profile?
and there are no other sync clients/software installed on the PC?
and there are only TWO MS Accounts in the picture – yours, which is also linked to Office 2013 itself AND your SkyDrive AND your OUC
and hers which is linked to her SkyDrive and her OUC
VG OneDrive video
Win 8.1 - ignore 'selective sync' and 'fetch'