MD5 is a One-Way Digest Algorithm
You can turn a cow into a burger, but you can't turn a burger into a
cow.
The purpose of a digest algorithm is to create a 'hash' which can be compared to another 'hash' to check if the inputs are probably identical, without revealing the actual inputs. This is why hashes are regularly used in databases to store passwords, because someone with access to the database will not be able to work out the actual passwords.
If you want to make sure that your usernames and passwords are communicated securely, you should use SSL to create a secure connection between your website and your user. Your web server will take care of decryption automatically.
On a side note, do not use MD5 to hash passwords, it's an old and vulnerable algorithm. Check out PHP's password_hash function instead. If using PHP prior to 5.5, ircmaxell has ported this for you.