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Usagi originally meets Luna by accident. On her way to school she sees a bunch of little kids bothering/beating something. She runs over and tells them to stop and Luna is revealed when they run away. As Usagi picks up the black cat, she notices a band-aid on its forehead. As Usagi peels the band-aid off, we get a glimpse of the moon crest there before Luna jumps up and runs away. In the manga, it is quite different. Usagi is running to school [late] and she runs over something. She checks to see what it was and it turns out it was a black cat! She peels of the band-aid, sees the crescent moon, and kisses Luna to show she is sorry. In return, Luna scratches up Usagi's face and runs away.
Luna becomes the Sailor Senshi's mentor and is the character that knows the most about what the Sailor Senshi are supposed to do as well as knowing much of the history of the moon kingdom, she can bring back memories using her "Luna Mind Meld". In the beginning she was referred to as a "party pooper" because she was too serious about things. That triggers her to get teased by Artemis.

Artemis was Mina's cat, before the existance of the Sailor Senshi. He gave Mina her transformation pen, so that she could fight the world's evils as Sailor V. So she was fighting evil long before Sailor Moon. Believing that the forces of the Negaverse would return to Earth, Artemis was an important guide to help Luna to find the other Sailor Senshi, giving them information about their location, etc.
Artemis is laid back, wild, and has a cool attitude. Later in the series, he and Luna have a kitten, Diana, who is Chibi Usa's guardian cat/mentor.

Since she travel's back almost a century, she has trouble understanding how everything works, so she ends up messing things around. She stays with Chibi Usa until the end of Sailor Moon Sailor Stars.