As part of an initiative called "Breakfast of Hope", they handed out on Wednesday 500 loaves of bread and rolls, as well as 150 pastries and cups of hot chocolate.
"We sought to restore a measure of dignity to people without a roof over their heads," Patricia Avila Kuljiš, the organiser of the initiative, told Hina.
Around 5,000 Croats and their descendants live in Bolivia, a South American country going through a social crisis.
Members of the community in La Paz decided to give gifts to their poorest fellow citizens on the occasion of Epiphany.
They set up street stalls covered with tablecloths in red-and-white checks, behind which they hung the Croatian flag.
"This initiative was not merely about giving food, it was a sign of humanity that further strengthens Croatia's reputation in Bolivia," said Avila Kuljiš.
"Our loyalty to this country and our solidarity with its families are unquestionable," she added.
A "solidarity shop" was also set up in the street, where poor Bolivians received clothing and footwear as gifts, according to their needs.
Around 530 people found something for themselves at the stalls.
The Croats also organised a "Cultural Bridge", a space where they spoke with Bolivians in the indigenous Quechua language, encouraging them to preserve their identity while bringing the two cultures closer together.
The initiative was financed by the Croatian families Blazicevic, Restovic, Mavric and Kuljiš who also volunteered in it. They have announced new and larger events.