La Unión is a municipality in La Unión Department of El Salvador. It is the capital city of the department of La Unión. It is the largest city in the d…La Unión is a municipality in La Unión Department of El Salvador. It is the capital city of the department of La Unión. It is the largest city in the department with a population of approximately 34,000 inhabitants. Previously known as Puerto San Carlos, it was renamed La Unión on July 13, 1824, after El Salvador gained independence from Spain and formed the United Provinces of Central America. La Unión became a department on June 22, 1865, and the city of La Unión became its capital.