Personally, I never liked using Illustrator for vector based layouts. Although it's an industry standard, I find it "boxy" and not terribly intuitive.

Having tried them all, I far prefer CorelDraw. It's cheaper and, IMHO much easier to use.

Vector based programs are most often used for print oriented layouts, those with complex shapes that need to be scalable and that require a higher level of precision. Raster based programs, like PhotoShop are intended to be used for photo oriented layouts that require less precision.

Either will work fine but I'd use PhotoShop to export your web graphics.

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