VLC whilst quite a capable product, has never seemed user friendly to me, by default not always properly correcting image quality or dealing with interlacing. Because no layman's guide to getting it working nicely seemed to exist (only a barrage of technical options), I found I quickly stopped trying to use it.
Similarly, I hope no-one is fooling themselves over open office. Whilst I totally admire the hard work, it is in no way a true competitor yet to MS Office. Writer (the word replacement) is adequate (although lacking grammar checking), Impress (the powerpoint clone) does all that you need it to, and there is no direct comparison for the Draw program (short of Visio, which is in a whole other league). Draw alone made the installation (and its continued presence after getting Office 2007) worthwhile, it is a wonderful application. However it has one major failing that says a lot about the majority of the development team. Calc (Excel replacement) is quite frankly only fit for simple spreadsheets, not for producing business-quality charts or more complex scenarios. They completely failed to understand the needs of the professional users of such software, in my opinion.
On a more positive note, since you were not adverse to suggesting online applications, then
Meebo is really an absolute must. Even if you generally prefer to use proper IM clients, it is invaluable when travelling, or when you have guests over who want to chat online.