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This may be the stupidest question anyone who's been making graphics as long as I have has ever asked but what is vectoring? I know its the pen tool but what drawing a triangle with the pen tool is hardly vectoring and some people say you can vector without pen tool knowledge so what is vectoring?
A vector, by definition, is a graphic which can be scaled infinitely. Photoshop is a mainly a raster program (ie, you lose quality as you increase the dimensions) but with the help of vector masks it works as well as a vector program such as illustrator.
I think the politically correct name for the vectors you're talking about is 'vexel art'. Vectors, like ritwikr said can be rescaled without losing quality. Adobe Illustrator seems to be the choice of the pros when it comes to vectoring but photoshop's pen tool is more than adequete for vectoring. I really want to get illustrator and start some more vectors, especially now that iv started graphics at college.