Misato's role in the series is as important as anything else.
She acts as the mother/friend/sister and everything else to Shinji who seems to have some problems with his emotions.
She is the commander of the EVA pilots and cares for them a lot.
Unlike Gendo who doesn't seem to care, Misato worries about the pilots and doesn't want to risk their lives.
The commander and chief officer of NERV, he is the one who decides what NERV should do.
He also is the father of Shinji but he doesn't show his affection to Shinji. He is cruel in a sort of way that he is willing to risk the lives of the pilots just to save what he has done.
He doesn't show much emotion but he was once a very kind man until his wife, Yui died. Since then, he has changed drastically and seem to care only for Rei who is said to be the clone of his wife.
The first time Shinji arrived at Touji's school, Touji bullied him right away punching him and knocking Shinji down.
But since that incident, they have been good friends. One time, in an angel attack, Touji's sister was injured and needed a lot of medical treatment which NERV could give.
The computer searching for possible pilots of EVA found that Touji was one of them. Touji accepted the job in exchange for medical help for his sister.
But this proves to be a fatal mistake because the EVA that he was piloting was taken over by an angel.
Gendo ordered to be destroyed with Touji inside. Shinji couldn't do it so they used the dummy plug and Shinji's EVA unit went berserk and tore the angel to pieces.
Touji survived but this accident left him without the use of his legs.
Kaoru Nagisa is a mysterious person. When Asuka wasn't capable of piloting her EVA, Kaoru was the one who substituted for her.
He surprised them all when he seem to have a perfect synchronization rate with the EVA unit.
Shinji and him became good friends until they discovered that he was an angel. Kaoru controlled the EVA unit even when he was outside of it.
In the end, he was about to cause the second impact when Shinji was forced to crush Kaoru who was his best friend.
Fuyutski Kouzou or just plain Fuyutski is the second in command of NERV.
He is kind of the best friend of Gendo and frequently advices Gendo Ikari about what to do in operations.
Unlike Gendo, he is more humane in a sense that he doesn't want taking risks which can lead to more casualties.
You can call Fuyutski as the conscience of Gendo.
Kaji is a spy for the Japanese Government. He is given the task of finding out the hidden agendas of the organization NERV.
Misato and Kaji were once lovers but that was in the past but they still seem to care for each other.
Asuka has a big crush in this Japanese Spy and you'll see her a lot of times talking about Kaji.
Kaji is also somewhat like a big brother to Shinji who seem to enjoy his company.
This blonde woman with a noticeable mole in her face is Misato's best friend.
You can see them together often advicing each other and also arguing with each other a couple of times.
Ritsuko Akagi is a very smart and intelligent woman which makes her one of the best scientists in NERV.
Ritsuko's mother is the the inventor of the three MAGI computers.