Resetting a Forgotten Root Password
If you have forgotten the root password it is possible to set a new one as follows:
Interrupt the boot at the GRUB stage and boot to runlevel 1, AKA single user mode. Interrupt GRUB by typing a character such as "space" then append to the kernel line by typing "a", backspacing through "rhgb quiet" and appending " 1<enter>". This will give you a root shell and not a login prompt. From there you can use the "passwd" command to set a new root password.
Other user passwords can be reset, and other administrative tasks can be performed as well. Exiting the single user root shell will boot to the multi-user mode defined in /etc/inittab.
CentOS-6 Note: Due to an upstream SELinux bug the root password cannot be reset on a fresh install of CentOS-6 without an additional step. Booting with "selinux=0" appended to the grub kernel line, or doing "setenforce 0" after logging in and before attempting to reset the password are work-arounds. This is corrected by applying already-released errata updates.