As told above, only when the ignition switch is on. 12 volts, or slightly higher when engine is not running, 14 or so when it is will confirm generator/alternator is doing it's job.
With everything working normally and an accurate volt meter: Turn on the key, battery should show between 12 and 13 volts ( a fully charged 12v battery is actually 13.2) Turn the starter, and the starter can draw the voltage down to 10 or so depending how cold it is, etc Engine starts, voltage to at least 13.2 Rev the engine a bit, should go to 14.5