A Serial ATA port multiplier is a device that allows multiple SATA devices to be connected to a single SATA host port. Many common controllers do not support this feature, as it is not a requirement for a SATA controller.
First off, I am assuming you are using a laptop, since the product you linked is an ExpressCard, typically found in laptops. Although, it would work on a desktop with an ExpressCard slot.
The product you linked is not SATA, its eSATA. That would mean you would need an eSATA enclosure to hold the two drives and provide power. It says right in the description it is a port multiplier, so it would work.
FYI eSATA and SATA are technically the same, its just eSATA has a different connector for external use.