PHP, as based on the fact that this is a PHP forum. But realistically, both are capable of being 'securely coded'. The real issue is the safety of the server and its exploits (IIS seems to have far more exploits than apache)
If the info is really senstive, use SSL encryption to secure the connection.
MD5 the passwords, set up the mysql accounts to the bare minimum needed (ie select, update, insert). If you can set the accounts to limit access to certain ip ranges