Since this is in "Game Programming" rather than "For Beginners"
MMO has a meaning. To reach the level of massively multiplayer you are going to need a budget of at least a tenth of a billion dollars, but more likely reaching a quarter billion dollars. Monthly expenses for running the servers are going to be a high six-figure or possibly a seven-figure dollar amount. If you are asking this type of question, MMO does not apply.
If you want to make an online game, that is easy. The networking forum FAQ has links to a project where they built a simple online game server and client in just a matter of hours.
You mention using HTML5 for your game client. That means the client will be relatively simple, and most of the effort will be in the server. For the client you need to learn HTML and JavaScript. You need to decide what languages and tools your server will be written in, I'm guessing a mix of C++ or C#, SQL, and probably something additional if you plan on automating your build chain. You could use PHP or anything else if you want, that is up to you. Since the game will likely be graphical you will also need assorted art tools for 2D art and some audio tools.
You mention using Unity for your game client. That means the client will be relatively complex. Although Unity does have some support for networking many of the components (such as physics) are not easily combined for synchronized network play. You will need C# skills (or one of the other languages Unity supports, but I recommend C#). You will also need modelers, artists, and animators for 3D, or you will need 2D art. You will need a matchmaker server if you intend to keep the processing on the client side, and since you are already using C# for the engine you could leverage that for your server. If you intend to do much more processing on your server you will probably want to pick up a few more things, SQL or some other data system for accounts and leaderboards, plus much more for whatever processing you have in mind.
I *STRONGLY* recommend that before you start making online games you build a few offline games. They are much easier and you will learn many valuable lessons that you can apply to your future projects.