The Qio BIOS software is not running and it must run to re-arrange the PCI busses. Because some PC's BIOS's do not allocate space for empty PCI slots, you may need to boot your PC with a card installed in one of the slots in the Qio. You can verify that the Qio BIOS software is loading by checking to see the Sonnet banner in the BIOS startup.
This is a Microsoft Windows driver bug with some 64GB CF cards. Sonnet is working with Microsoft to resolve this issue. (64GB and 128GB CF cards work fine with Qio and Qio-CF in OS X.)
A partial list of cards Sonnet has tested:
Patriot Pro CF 266x 64GB/128GB card is recognized under Windows
Lexar Pro 1000x UDMA 7 64GB/128GB card reports itself as 32GB
SanDisk Extreme Pro UDMA 6 64GB/128GB card reports itself as 32GB