I have new iPhone 4S with iOS 6.1.0. Can I upgrade my current iOS version to 8.0.2?
Whether there can be a problem that I skipped iOS 7 and jump straight from 6 to 8 version?
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There won't be a problem.
I'm not 100% sure that upgrading to iOS 8 will be in your best interest, though, because I've seen lots of reports of people with 4Ss having performance problems on iOS 8.