The ambient dose equivalent rate H*(10) was determined at various locations in the metropolitan area of the cities of La Paz and El Alto in Bolivia. A NaI(Tl) scintillation detector was employed to infer the gamma-ray fluence, and the fluence was transformed in dose rates by means of the appropriate coefficients. In this paper, a full methodology for the estimation of dose rates associated with gamma rays emitted from the ground (terrestrial radiation) and the atmosphere is developed from measurements made with the scintillator instrument. The energy calibration and resolution of the apparatus are presented, followed by the estimation of its response and efficiency by means of Monte Carlo simulations. Lastly, the definition of H*(10) is used to determine the conversion coefficients needed to transform gamma-ray fluence in dose rates. With this methodology, rates for H*(10) around 123 ± 8 nSv/h were estimated using data collected in three city districts: Mallasa (3320ma.s.l.), San Antonio (3620ma.s.l.), and Zona Sur (3400ma.s.l.). The dose rates are believed to be representative of the terrestrial radiation fields encountered in the highlands of Bolivia.