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I am obtaining 3 LORs. One from my work supervisor, volunteer supervisor, and my last one is going to be from an instructor... for some reason my UG has a lot of grad students teach (even the 4000 level courses). Does it matter if I get my 3rd LOR from one of my instructors that is a grad student? Of course the letter will address my academic ability, etc but does it matter who it comes from?

Thanks!

No, as his LoR will be as a person who saw you as a student, in (a close to) a professor-like capacity. Just make sure that he can speak about your academic abilities and will also specify what his role was to do so.