The first time she saw him was when she found the Aether and it took her to a cold, underground base. She walked inside with caution, hearing the echo of her steps. She saw something that took her breath away. There were freeze chambers, and he was in one of them, with a mask covering half his face and wires all around his body, he wasn't the only one though, there were five more, but he must have been the most important of them all because he was in the centre of the room. She heard someone approaching and she tried to find a place to hide or to escape. And then the Aether took her back to London. She never talked about it to anyone.
Then she learned about him. She was trying to forget the incident back then. But Captain Rogers approached her so she couldn't escape knowing about him again. After the fall of SHIELD, there were few people to trust in. Steve trusted Thor and Thor trusted her even though their romantic relationship was over. Steve told her he was searching for a person, his old friend, turned into the infamous Winter Soldier. He even gave her a file with a lot of information and begged her that if she saw 'Bucky', called him immediately. At the beginning she didn't know why he was trusting in her until he mentioned Thor and how she would understand things. And she did. She understand what Hydra did to Sergeant Barnes after reading the file. It was horrible. To have all your mind wiped out and then turned into a killer machine without your consent, to be waken up and put to sleep again. She knew how it was to be controlled.
He caught a glimpse of him in Bucharest. She was there for a scientific meeting and they were taking a break to eat. She went outside the University so she could admire the city a little more. And she saw him buying some coffee and then leaving quickly, as if he wanted anyone to notice him. Before calling Steve, she had to be sure it was Barnes. She followed him through the streets, leaving a proper distance so he couldn't see her. Of course it was him, it has been years looking at his photographs, her eyes couldn't lie. She almost walk through the whole city until he got in an apartment building. There she stopped, it would be too dangerous as she didn't know how he will react, he didn't even know her. It was better to call Captain Rogers. Too late. That evening, she heard the news about Vienna. No, he couldn't have been in two places at the same time. She was damn sure he was innocent.
Jane finally met him. It took a few years to the Team to reconvene. To forgive each other. Now, they were facing a new and dangerous threat, one they could never imagine and they needed to be together. She was there because Erik called her, the Avengers needed all the scientific help they could get. She was introduced to the whole team, she knew most of them and she knew him well, of course, but she didn't say anything. He looked really different. He wasn't Sergeant Barnes nor the Winter Soldier nor the guy she saw in Romania. He wasn't any of them. He had shorter hair, a different metal arm but the most important: he looked alive. In those nights in the Avengers facility, when she couldn't sleep, she just went to the kitchen for a glass of water and then outside to see the stars. And every night he was there, he still couldn't sleep. They talked just a bit the first days about random facts. She didn't know how to adress him and he told her to call him 'James'. James. James. James. She couldn't stop repeating his name. When they were becoming closer, it was time to face whichever enemy was there in outer space. But after everything was finished, there was no doubt they would meet each other again.