When the War of Independence broke out, he participated in naval operations against the forces of the Ottoman Empire.

After independence was achieved, Voulgaris became involved in politics as a bitter opponent of Governor Ioannis Kapodistrias.

Voulgaris was involved in the coup against Otto of Greece in October 1862 and became Prime Minister once more.

("Τις πταίει;") in the Athens daily "Times" ("Καιροί") concerning the waste and corruption of the government.

Many of his associates were indicted on a variety of charges and Voulgaris himself took ill and died in Athens on 10 January 1878.