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In the TV series The 100, initially only Jaha could see A.L.I.E. and nobody else, and he communicates with her.

Secondly, anybody who takes the key to the city of light (that blue star pill) is also able to see the A.L.I.E. - this is evident when Raven takes the pill. She didn't see A.L.I.E. before taking the pill, but afterwards she saw her and even communicated with her.

Raven not able to see A.L.I.E.

Why does Murphy see and communicate with A.L.I.E. (who is a hologram) even though he has not taken the pill, but others can't unless they take the pill?

Picture below shows A.L.I.E. in the presence of the chancellor, who has not spotted her:

Jaha, the chancellor, and A.L.I.E.

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This is fairly simple, OP even stated the anwser in his question. When Murphy see her, she is an hologram inside the mansion, meaning she uses an holographic device to communicate with her new guests. Once they take the pill, the holographic program is able to make you see her while others who didn't take the pill won't be able to.

If I'm correct, this is the only time Murphy sees her.

TL;DR : Two ways to see A.L.I.E. 1- Be near a holographic device that she controls 2- Swallow the pill

EDIT: I'm not 100% up to date with the latest season, if you mean Murphy has actually seen her without taking the pill and outside the mansion, please inform me I will retract my anwser.

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I think it's because he entered the mansion. He sees her in there, just like Jaha, even if both didn't take the pill but entered the mansion. There's no other way that would make sense to me

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    We prefer answers with evidence. Can you cite anything or even give any more information on why you think you are correct?
    – Meat Trademark
    May 12, 2016 at 0:30

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