答案是their,其实分析一下句子结构不难看出,who引导的定语从句先行词为：students.
因此为了使定语从句里面前后一致,who是代表复数,那么相应的就须选择their.
顺便帮你解读一下这句子吧.
这句话中的确且只有一个定语从句,就是who,I am sure,always do their best.修饰先行词students.I am sure是一个插入语,把其去掉也不影响句子结构的.也是简化版的定语从句是：who always do their best.明白了吗?
he is one of the students who,I am sure,always do_____best.
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