I presume you really meant Outlook Express and NOT Outlook...
Outlook Express does NOT use PST files, rather DBX files for EACH folder you create...
However, the file size is probably still the issue as the others have intimated...
You should locate the folder in your profile containing the "xxx.dbx" files (where xxx is the folder name) and make sure they are small enough to manage. If they are not overly big, try compacting your folders and cleaning up your recycle bin and temp folders to make more hard drive room.