Buying vouchers which is the premium currency of the game will enable you to unlock any hero and add them to your stable of included characters. If you do not want to spend real money on purchasing vouchers you can get some free by going to the main menu screen and selecting the 'Road To Glory' option. This feature will allow you to unlock up to two heroes per day, many of which are suitable for beginners. If you play three matches you will get a hero. do that twice and you will get two heroes. If you keep repeating this you can get up to 8 heroes for free, there is no other way to unlock these heroes outside of play. There is no need to do the big 5v5 matches, the smaller 3v3 skirmishes will also count toward the goal. Those only take a few minutes each.
Another 4 Heroes can be unlocked by playing matches with friends, they become unlocked at the first win, third win, sixth win, and finally at your tenth win. Only matches won in Standard 5v5 Grand Battles counts towards unlocking them. This means that wins in Ranked games and other modes do not count. In total 'Arena of Valor' gives you 14 heroes for free, 2 through tutorials, 8 through Road to Glory, and 4 more by winning 10 matches with friends.