Lithium batteries are only 3.7V (3.6 at first and 3.8V now), which is the rated voltage. 4.2V is the charging termination voltage of lithium battery, which can be understood as the highest voltage.
The same lithium battery has different voltages at different power levels. Approximately between 3.0 and 4.2 V, 3.0 V is the end of discharge voltage and 4.2 V is the end of charge voltage.