If you are to meditate every day, then doing so first thing in the morning should become a habit. This is mainly because your morning routine is going to conveniently set the tone and the rhythm of the entire day. Right before breakfast is an ideal time to go ahead and meditate.
Keep in mind, though, that meditation could be quite daunting for beginners. So, at a start, it might be a good idea to focus on deeper and slower breathing techniques even if you had to do it for just five minutes after you wake up right before you get busy.