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I have personally tried this on one of my systems. The partition table on the 64GB SSD will be lost, thus resultingly in the loss of your OS.
If i were you, I'd do the following:
1) Clone the OS and drivers to the HDD
2) Disconnect the SSD and boot from the HDD to verify the clone worked
3) Upon confirmation that the HDD boots, connect the SSD and delete its partition using disk management in windows.
4) Then enable Smart Response Technology.
Note: I hope you installed the original Win7 OS with the BIOS in RAID mode (not AHCI mode). Otherwise you will need to reperform the OS install. Smart Response requires that RAID mode is enabled in the BIOS.
Many thanks for this - you've pretty much confirmed what I expected. It looks like the slightly longer way around to fix it than I had hoped, but at least I will be able to make full use of the 64GB for caching.