I prefer Photoshop over Fireworks, but that's more a matter of what I'm used to. There are other designers who prefer Fireworks so it's really your choice. When Photoshop and Fireworks were made by two different companies, Adobe and Macromedia respectively, the designers' preference came down to Adobe or Macromedia products. Since I learned on Adobe, Photoshop was my go-to software. Even now that they come together in CS, I still use Photoshop and have never opened Fireworks. I use Illustrator for all of my vector work as well.
You could also look into free options like GIMP. Although, I've never used it myself, there are some designers that like it.
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