Yes, that would work. You have to save it to a data disk as an intermediate step, and make bootable media.
Alternatively, you could use any free clone software. Download the software, make a bootable CD or thumb drive, boot to the utility, and clone small SSD to big SSD. Remove small SSD from system or just use the BIOS to ensure that the system boots from the new one. Once the system is stable, reformat the small SSD and use it for whatever data you want to be fast. Even scratch space.
A very frustrating day, my Win 7 was an upgrade so neither it nor restore disk worked, XP wouldn't install on a Samsung 830 series 256 gig SSD it order to do a clean install. With just the two new SSDs I could see them both quite nicely and read and write a file to the new one. I eventually came across clonezilla which worked quite nicely but I have a 300 gig Raptor and a 2 Terabyte whatever which ended up with the wrong drive letters. I had to remove the page file before it would let me change the drive letters back. The old SSD will go and sit on the shelf, I've run out of SATA connections by the time I have my other hard drives and DVD drives connected.