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The reason he first approached her was because she was safe, because she couldn’t touch him. However much she obviously wanted to.
That and because she hacked an arm off the ogre that almost flattened him which was as good a recommendation as any other.
But her heart has been fixed. She’s been hugging everyone in the blighted inn, lifting them off their feet.
Her hands worked over Astarion’s ass and thighs and she whispered such enthusiastic filth in his ear and…
It had been a long time since he’d really wanted to please the person fucking him. And now, with Karlach smiling down at him, her hands on his thighs, he felt like he’d failed before he’d even begun. Because if she found out, if she knew he didn’t want as she did then…
She couldn’t find out.
So Astarion plastered on his smile and kissed by the book.