Posts are sequenced chronologically, with newer posts appearing at the top. If you want a particular post to be always at the top (sticky post), you will have to play with the dates. When you create that sticky post, at the bottom, click POST AND COMMENT OPTIONS, then predate your post to the latest possible, as shown in the screenshot above.
UPDATE 21 January 2007: For the New Blogger (formerly beta), see posts New Blogger (formerly beta): How to add AdSense or sticky post, etc. at the top of every page of your blog.
Book: Blogging for Dummies
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