The 32-year-old actress - who appeared alongside the 30-year-old star in 'Gossip Girl' and dated him from 2008 to 2010 - admitted she hopes the allegations are ''untrue'' after he was accused of sexual misconduct by three women, Rachel Eck, Kristina Cohen and Aurélie Wynn.
Jessica said: ''[I] wasn't there, for either side, so I can't say it did or didn't happen. But I know him well and I've known him for years, and I found it shocking.
''I hope that it's untrue, but I also feel bad for anyone that's been in that situation, for the women that have to deal with that, for the situations that are true.
''I don't know those girls at all, and they could be lovely and awesome and all that. From the Ed I know and working with him for five years and having a friendship through all of that and after, it was shocking. It was shocking.''
Jessica has spoken to the 'White Gold' star - who has hit out at the allegations against him as ''provably untrue'' - since the claims were made and admitted it has been ''tough on him'', and questioned whether the alleged victims could be ''stretching the truth''.
Speaking to Cosmopolitan magazine, she added: ''I have known Ed for years and know how lovely he is, and don't think he would ever put someone in a position like that.
''It's difficult, because you don't want someone you know to go through that or do that to someone, or knowing them well, knowing that you don't think they would, and you don't want, for the girls that are coming forward, it's like, are they stretching the truth?
''It's just, it's a touchy, tough thing that you pray it's not true.
''You know, he's like, 'The truth will come out and hopefully people see that and hopefully that's it.' It's just such an unfortunate thing all around.
''And I have to be so careful, because it's not my situation and I don't ... I wasn't there. So it's hard to speak on behalf of those girls or him.''
Earlier this month, Kristina accused Ed of sexual assault, claiming the star had ''held [her] down and raped [her]'' after she fell asleep in a bedroom in his house.
Shortly after the claims, Aurélie then alleged a ''similar'' ordeal happened to her when she visited Ed's home with her boyfriend at the time, Mark Salling.
Ed then took to social media to deny the claims.
He wrote: ''It is disheartening and sad to me that as a result of two unverified and provably untrue social media claims, there are some in this environment who could ever conclude I have had anything to do with such vile and horrific conduct.
''I have absolutely not, and am cooperating with the authorities so that they can clear my name as soon as possible.''
A third woman, Rachel, has since claimed Ed had pulled her onto a bed and ''aggressively groped [her]'' when they were at a party.
She alleged he would ''try to kiss me or kind of push me up against the wall'', and although she ''pushed him off'' each time, she claims ''it got worse and he got more handsy'' as the night wore on.
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