Given the importance of body composition in maintaining optimal physical and functional capacities, the use of appropriate, field-based assessment tools should be a priority to assist in maintaining the occupational safety of firefighters and the community. For ease, body mass index has often been used to assess these changes. However, it is limited in its accuracy. The purposes of this study were twofold: (a) to compare the validity of different measures of body composition against dual-energy X-ray absorptiometry (DXA) in urban firefighters and (b) to assess these measures in their ability to provide meaningful interpretation of criteria-driven categories of adiposity. A total of 64 male firefighters (age = 44.0 ± 9.5 years) underwent full anthropometric profiling (predictor equations used to determine body fat percentage [BF%]), bioelectrical impedance analysis (BIA), and DXA assessments. Participants’ body mass index was calculated, and BF% and lean mass were determined along with criteria-driven categorizations of adiposity. Anthropometric (skinfolds) predictor equations (e.g., mean bias = −4.4% for BF%) were typically closer to DXA measures, compared with BIA (9.4% for BF%). However, when determining categories of criteria-driven adiposity, BIA (42.9% overweight or obese) provided closer estimates to the DXA-determined distribution (44.6%) than anthropometric-based measures (up to 40%). Body mass index appears an inappropriate measure for accurately determining categories of adiposity with 64.1% classified as overweight or obese. Given the logistical constraints of anthropometric profiling, and the closeness of BIA to DXA in adiposity categories, BIA may be a suitable alternative to DXA for assessing body composition in professional urban firefighters.