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PDF documents are automatically retrieved when you use the Zotero Connector, this is the best way to add items to your library. However, if you have PDF files already saved on your computer and you want to add them to your library, Zotero Desktop can create a bibliographic record from the PDF.
Simply drag the PDF file into Zotero library central pane, this is also the easiest way to attach a PDF file of an article to its corresponding entry in your library:
Alternatively you can attach files to an existing item in this way:

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If you have PDF files stored on your computer, you can drag the files into your Zotero library. If the PDF has a DOI, Zotero will automatically find the 'metadata' or bibliographic information and populate the relevant fields.