Shiki does kind of have a 'shoot first, ask questions later' attitude. He's nice enough under normal circumstances, but when threatened he tends to do what he needs to in order to survive without question, and unless the enemy is someone he personally cares about (which, admittedly, happens to him more often than you'd think) killing them tends to be his first option. It's not hard to see Shirou having a major problem with that.
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