No, we cannot directly separate alcohol dissolved in water using a separating funnel because alcohol is completely miscible in water.
A separating funnel is used to separate only those liquids which are immiscible.
But, we can use the process of distillation to separate alcohol dissolved in water.

Distillation is used to separate different compounds. The concept of distillation is the different boiling points of the liquids in a mixture. That means a more volatile compound will evaporate at a lower temperature than a less volatile compound at the same temperature.