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Im wondering - can i use my Sonos Arc (placed under TV) as primary speakers and then use my Sonos Amp (With connected speakers) as surround ?

Arc is connected via ARC from TV - Amp via Wifi...

If you mean your Sonos Amp, then yes.  Please see https://support.sonos.com/en-gb/article/set-up-your-sonos-amp

Edit: Now with the correct link!