Kenpachi Zaraki the demon captain
Neji first met Kenpachi over the LPs, but met him in person not too long after. He's not quite afraid of him, but there is a very small part of him that is slightly intimidated; Kenpachi is at least a foot taller than him, weighs a lot more and also smashed in the side of a tree that Neji had been leaning on. He didn't show it at the time (and never will), but he's wary.
Cissnei the fighter
Cissnei and Neji met when Neji first arrived on the island; she told him about the LPs and Network and he was grateful. The most time they spent together in one sitting was during the Heartless event. She and Neji set up a healing station that he was in charge of and even fought side by side against Heartless. They could be called friends, but allies is a better word.
Aoyagi Ritsuka the mature child
Ritsuka was the other one that greeted him when Neji first arrived on Salkia. He didn't really understand (still doesn't) why Ritsuka has cat ears and a tail, but he doesn't question it. Though, he is rather curious about how Ritsuka is so mature for his age.
Tsukino Usagi the little sister; moon princess
Neji and Usagi first met when Ritsuka introduced them. The first time they met face to face was during a monsoon on Salkia and the lights had gone out. Usagi thought he was a sailor scout at first, but he explained the whole ninja thing and she understood. Neji sees Usagi as a little sister and will do anything to protect her. He's also one of the only people that know about her secret identity and he protects that very well.