So why is she targeting him again? The pirate looking dude makes it sound like she really ...

Yea I don't get how they're connected either. Why does she call him his "little brother" and that they should finish a talk they couldn't have "back then"? She talks as if they're pretty close, yet I don't remember her from a previous chapter.

They spoke in chapter 113. Since both of em were abandoned they called each other siblings. Mc said he wanted to be like her. So She later got pissed of as although they were abandoned, there circumstances afterwards werent same. So she decided to teach him a lesson.