I've just bought a Pioneer DVR-108, I've already got an existing DVD player.

the question is can use the two drives together on the existing cables connected to my motherboard?

Cheers

Sure. Ideally you would want each on its' own cable. If that is not possible, if one is a RW it should be Master & the other Slave, tho in some cases the manufacturer suggests setting both to Cable Select. Your Pioneer manual should have some info.

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