I'm assuming the repeated <html>
tags in your example are just placeholders and would actually be <div>
s and other elements making up the actual content of the page.
Your example is what's commonly called "spaghetti code" because it can quickly turn into an unmaintainable mess because you can't clearly see an overview of the HTML, nor can you see all the PHP code in one place.
The main thing to keep in mind is separating application logic (such as your database queries) from presentation (HTML and presentation logic like looping over an array to display it as an HTML list).
At the very least you'd want to put the main PHP code at the top of the file like you said, but it would be much better if it was in a separate file.
P.S. Any beginner book on PHP will discuss this in detail.