Maes Hughes is a silly, family-obsessed, and sometimes serious man. He is very serious when it comes to his work, but at the same time very obsessed (in a good way) with his daughter and family. Throughout the anime, he is often seen befriending people, and giving Ed, Al, Winry, and even Roy Mustang advice. Towards the beginning of the series, he is shown very excited about his wife being pregnant. This even resulted in Ed coming to Hughes' house to meet his wife. He sometimes shows his more sensitive side to characters throughout the series.
Hughes is often shoving pictures of his daughter into people's faces, which often annoys them, but in a silly way. This shows how much he loves his family, but is often suggested he does this to get away from his job, which can be quite depressing at times.
Said by many to be the saddest moment in the series is the death of Maes Hughes. Before his last moments, he had dropped a picture of his wife and daughter, which symbolizes what a loving husband and father he was. He had figured out that his subordinate helping him was an undercover Homunculus (who had the ability to mimic people's appearances), and then slit its throat, saying the words "Forgive me, but I have a wife and child waiting at home". Only seconds later, Envy (the Homunculus) gets back on his feet, transforming into the image of Hughes wife. This stuns Hughes, as he is unable to attack for the few seconds that Envy needed to shoot, and ultimately kill Maes Hughes.