Werner seems to appear as her conscience while she is with Ilsa, but he doesn't appear like this anywhere else, even though she could use him at other times
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Ilsa really gives Liesel the tools to read and write. In many ways Ilsa helps free Liesel through writing and literature. Ilsa's library is sort of a heaven for Liesel. Liesel loves the written word. My take is that heaven is also where Liesel imagines her brother. It is fitting that she should see him in a library.