Its name honors the Bolivian diplomat and foreign secretary Rafael Bustillo († 1886).

The capital of the province is Uncía with a population of 5,709 in the year 2001, the largest town is Llallagua with 20,065 inhabitants.

The province extends over 70 km from north to south as well as from east to west.

The main language of the province is Quechua, spoken by 86%, while 74% of the population speak Spanish.

The people are predominantly indigenous citizens of Quechua and Aymara descent.