The easiest way to get free website navigation buttons is to download them from one of the many sites where such buttons are available. In some cases the navigation buttons are part of a larger button pack, while in others they constitute a separate package.
Free website navigation buttons are available in different styles and color palettes. For instance, if you are looking for Web 2.0-style free website navigation buttons, this free arrow pack contains some buttons you can use. The buttons can't be used right away because they are in .psd format, which is the default Photoshop file. You need to use Photoshop to make them into .png, .gif, or .jpg before you add them to your site but the advantage of their .psd format is that you can modify them if you need to.

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Another good pack of free arrow buttons can be found
here. This pack of small, square arrows includes free icons in 8 colors.

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If you're looking for more than just arrows, you might want to check out this pack of 165 website icons from GoSquared!

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When you find a pack of free website navigation buttons, before you put them to use, read the license. In many cases the buttons you have just downloaded are really free and you can use them without any worries. However, be careful because in other cases the commercial (or any) use of the buttons in your designs might require something in return – to mention the site, or a back-link, or something else. This is why you need to carefully read the license, so that you don't unintentionally violate it.