Inkscape
We exclusively use Inkscape, which is open source and thus free. The latest version of Adobe Illustratorsave to SVG well as well, and i asume CorelDraw does as well. As of now I intend not to purchaselicenses for these programs to have at the office, but I am willing to reevaluate that decision ifpublic outcry is too large.
No matter what you plan to work with or specialise within, as long as you are doing any kindof front-end development you must be able to perform simple task on SVG files. Inkscape iswonderful and free.
The main important thing to grasp is prototyping websites, webapps and user interfaces in Inkscape.These can then easily be sliced apart and use as the graphical foundation for HTML and CSS realisation.Several of the books below have good sections on designing for the web in Inkscape, but there are alsonumerous good tutorials on the internet. The most important concept is to make sure everything snaps to pixels, whichis usually easiest done using a grid. Since Inkscape is vector based you can place nodes inbetween actualpictures which make them render poorly (unsharp) when used on the web.
Specific tutorials
Using the perspective tools and more: http://ahninniah.blogspot.se/2013/05/drawing-in-perspective-with-inkscape.html