Libraries

Ninite
Get free programs in one quick, easy install. Includes Notepad++, VLC, browsers and Paint.net.
http://ninite.com/
Gizmo's Freeware
The go-to place for software programs.
http://www.techsupportalert.com/

Production

X-Mind
Useful for website mapping and flow chart design.
http://www.xmind.net.com/
Balsamiq
Create quick and easy mock-ups of websites in a cartoon format.
http://www.balsamiq.com/
Jing
Jing Project is a quick and easy screen recording software with reasonable audio recording capabilities.
http://www.jingproject.com/
Super
The best video converting tool that I know of. It looks like something out of the 80's but runs brilliantly.
http://www.erightsoft.com/SUPER.html
BrushEesy
Design brushes for Paint.net and photoshop.
http://www.brusheezy.com/brushes

System Tools

PCDeCrapifier
Remove pointless programs from your machine.
http://www.pcdecrapifier.com/
PreyProject
Add this to laptops to track them if they are stolen.
http://preyproject.com/
Microsoft security services
Free antivirus.
http://www.microsoft.com/security_essentials/