There are probably dozens and dozens of ways for approaching the initial stages of creating a website. You could sketch out the entire concept on paper, use Photoshop to create a beautifully rendered visual representation of what the site will look like, or cut your teeth right away on some nice HTML and CSS coding. I’ve used all of these different techniques to varying degrees in the past, and they have all proven useful in their own ways.
So, is there one right way to go about this? Yes! The best way to mock up a website is to use the technique that will be the most effective for your particular project.