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If some people at your workplace reject linkedin invites, does this mean they don't like you?

You should confront them and ask them. That is the only way to find out the truth.

Maybe you should try to get them to endorse you for something like "being an asshole" to find out what they really think about you.

Challenge them to single combat

I feel like these ideas are funny conceptually, but would only be awkward practically.

sometimes I think it has to do with whether he/she believes your a valuable connection in the future. I've had a few people from college try to connect with me but I can't see them as a potential resource in the future so I just leave their invite alone..

The only reason I care is because if I did anything to make someone uncomfortable or feel offended, I would want to adjust my conduct to be less of an asshole if we work together.

wtf kind of asshole would reject a coworkers linked in request?

maybe he didn't know you? do you have a photo? if not, he might not know your name

Otherwise, maybe he clicked wrong so you should send another one?