I used OpenOffice a lot both at work and at home. I'd say it is 97% identical with MSOffice, only it's for free

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I found it to be an excellent program and loved that it opened any old files made with MsOffice, while MsOffice doesn't 'know' the OpenOffice extensions and can't open files made with the latter. So here's a piece of advice

- if you want the OpenOffice files to work with MsOffice too, you have to be careful when saving them to indicate what type of file you want (respectively you'll choose .doc and .xls)
I don't use Excel too much but I work with a few basic formulas for getting various calculations made in a table/spreadsheet. OpenOffice does them all too, the ones I need

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In my opinion, learning how to use Excel is equally easy with both programs as the basic menus and commands are the same.
Good Luck!