Definitely Captain America and Agent Coulson. Captain America represents the old - school heroism of the Avengers and Coulson is the heart and soul of Agents of Shield. Their different leadership styles and moral compasses would create a great dynamic. They could learn from each other, like Coulson teaching Cap about modern technology and Cap teaching Coulson about the values of the past.
I think Daisy Johnson would be really interesting. She has her unique powers and a complex backstory from her time in SHIELD. In a crossover, she could interact with the likes of Thor. Maybe she could learn some new ways to control her powers from him, as he has experience with his own godly powers. And she could also show the Avengers her skills in combat and stealth that she learned in SHIELD. It would be fascinating to see how she holds her own among the super - powerful Avengers.
Loki could be a great focus in a fanfiction involving both. He has a history with the Avengers, but his wily and unpredictable nature could lead to some interesting interactions with the Agents of Shield. He could be playing his own game, pretending to help both groups while actually having his own agenda. It would be fun to write about how the Agents and the Avengers try to figure out his true motives and keep him in check.
Daisy Johnson from Agents of Shield would be really interesting. Her own Inhuman powers make her a natural bridge between the two groups. She could help the Inhumans understand the ways of Shield and vice versa. Also, Black Bolt from the Inhumans is fascinating. His power is so extreme that just speaking could cause destruction. How would he interact with the Agents of Shield? What kind of strategies would they have to come up with to communicate with him? It would be really engaging to explore.
I think Natasha Romanoff and Melinda May would be an interesting pair. Both are strong, badass women with a lot of combat experience. They could share their stories of their past missions, and also train together. Maybe they could even have a friendly competition to see who is better at hand - to - hand combat or espionage.
I think the interaction between Coulson and Captain America would be really interesting. Coulson is a big fan of Captain America, and Steve would be impressed by Coulson's leadership and the way he holds his team together. They could exchange stories about their different experiences in the war - Steve from World War II and Coulson from more modern conflicts.
Definitely Coulson. He has such a rich backstory and his relationship with both the Agents of Shield and the Avengers (in an indirect way) is very interesting. His resurrection in Agents of Shield also provides a lot of potential for fanfiction. You could explore how he copes with being brought back to life and his new purpose.
I think the interaction between Bruce Banner and Fitz - Simmons would be fascinating. Fitz - Simmons are brilliant scientists, and Banner is a scientific genius himself. They could collaborate on some new scientific research, like finding a way to control the Hulk better or developing new energy sources. Also, Clint Barton and Skye could have an interesting dynamic. Clint's no - nonsense approach and Skye's hacker - turned - agent background would make for some great banter and teamwork.
Hulk would be an interesting character to focus on. Imagine the dynamic between him and Wolverine. They both have superhuman strength and a bit of a wild side. Their fight could be epic, but then they could also form an unlikely alliance. Also, Black Widow could add an element of mystery and stealth to the story. Her skills in espionage and combat could be useful in a plot where the team is trying to uncover a secret conspiracy related to Wolverine's past.
Batman and Black Widow would be really interesting. Batman is all about mystery and detective work in the shadows, while Black Widow is a master spy. They could learn a lot from each other's skills in stealth and intelligence gathering. Also, Thor and Batman could be a great focus. Thor with his god - like powers and Batman with his human ingenuity. Imagine Batman trying to figure out the science behind Thor's hammer while Thor is amused by Batman's determination in the face of the supernatural.
Thor is another popular Avenger in fanfiction. His god - like powers and his fish - out - - of - water moments on Earth are fun to explore. And from Agents of Shield, Fitz and Simmons are beloved for their scientific genius and their endearing friendship that often gets tested in different fan - made scenarios.