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That adapter should be fine for getting a stereo signal out from a scart socket. You would connect an rca plug to the L and R sockets (adapter set to out of course) and the other end of the cable would go into your hi-fi or a headphone amp. The cable would be either 2 rca plugs on each end ; or 2 rca plugs one end and a 3.5mm stereo jack plug the other end.
If I understand you are expecting to plug your headphones into this adapter I don't think that would give you what you want as the L/R feed is designed to be amped by a hi-fi or av receiver etc.
Using the adapter to connect to your hi-fi would be the quickest test. Or check with your tv specs to make sure the tv scart puts out a stereo signal first before spending on cables, amps etc.
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