Files with .PST extension represent Outlook Personal Storage Files (also called Personal Storage Table) that store variety of user information. User information is stored in folders of different types that include emails, calendar items, notes, contacts, and several other file formats. PST files are used for archiving emailing data offline that can be later loaded and viewed in various applications.
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XLSX is well-known format for Microsoft Excel documents that was introduced by Microsoft with the release of Microsoft Office 2007. Based on structure organized according to the Open Packaging Conventions as outlined in Part 2 of the OOXML standard ECMA-376, the new format is a zip package that contains a number of XML files. The underlying structure and files can be examined by simply unzipping the .xlsx file.
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You can also convert PST into many other file formats. Please see the complete list below.