The built environment is an important factor associated with physical activity and sedentary behavior (SB) during adolescence. This study presents the methods for objective assessment of context-specific moderate to vigorous physical activity (MVPA) and SB, as well as describes results from the first project using such methodology in adolescents from a developing country. An initial sample of 381 adolescents was recruited from 32 census tracts in Curitiba, Brazil (2013); 80 had their homes geocoded and wore accelerometer and GPS devices for seven days. Four domains were defined as important contexts: home, school, transport and leisure. The majority of participants (n = 80) were boys (46; 57.5%), with a normal BMI (52; 65.0%) and a mean age (SD) of 14.5 (5.5) years. Adolescents spent most of their time at home, engaging in SB. Overall, the largest proportion of MVPA was while in transport (17.1% of time spent in this context) and SB while in leisure (188.6 min per day). Participants engaged in MVPA for a median of 28.7 (IQR 18.2–43.2) and 17.9 (IQR 9.2–32.1) minutes during week and weekend days, respectively. Participants spent most of their day in the leisure and home domains. The use of Geographic Information System (GIS), Global Positioning System (GPS) and accelerometer data allowed objective identification of the amount of time spent in MVPA and SB in four different domains. Though the combination of objective measures is still an emerging methodology, this is a promising and feasible approach to understanding interactions between people and their environments in developing countries.