This study examined the relationship between the neighborhood food environment and the food purchasing behaviors among adolescents. Grade 7 and 8 students (n = 810) at 21 elementary schools in London, Ontario, Canada completed a questionnaire assessing their food purchasing behaviors. Parents of participants also completed a brief questionnaire providing residential address and demographic information. A Geographic Information System (GIS) was used to assess students’ home and school neighborhood food environment and land use characteristics. Logistic regression analysis was conducted to assess the influence of the home neighborhood food environment on students’ food purchasing behaviors, while two-level Hierarchical Non-Linear Regression Models were used to examine the effects of school neighborhood food environment factors on students’ food purchasing behaviors. The study showed that approximately 65% of participants reported self-purchasing foods from fast-food outlets or convenience stores. Close proximity (i.e., less than 1 km) to the nearest fast-food outlet or convenience store in the home neighborhood increased the likelihood of food purchasing from these food establishments at least once per week by adolescents (p < 0.05). High fast-food outlet density in both home and school neighborhoods was associated with increased fast-food purchasing by adolescents (i.e., at least once per week; p < 0.05). In conclusion, macro-level regulations and policies are required to amend the health-detracting neighborhood food environment surrounding children and youth’s home and school.