This study aimed to compare the use of the bioelectrical impedance device (BIA) seca^® mBCA 515 using dual X-ray absorptiometry (DXA) as a reference method, for body composition assessment in adults across the spectrum of body mass indices. It explores the utility of simple anthropometric measures (the waist height ratio (WHtR) and waist circumference (WC)) for the assessment of obesity. In the morning after an overnight fast (10 h), 30 participants underwent a body composition DXA (GE iDXA) scan, BIA (seca 515), and anthropometric measures. Compared to the DXA reference measure, the BIA underestimated fat mass (FM) by 0.32 kg (limits of agreement −3.8 kg, 4.4 kg); overestimated fat free mass (FFM) by 0.43 kg (limits of agreement −8.2 kg, 4.3 kg). Some of the variation was explained by body mass index (BMI), as for FM, the mean difference of the normal range BMI group was smaller than for the overweight/obese group (0.25 kg and 0.35 kg, respectively) with wider limits of agreement (−4.30 kg, 4.81 kg, and −3.61 kg, 4.30 kg, respectively). There were significant differences in visceral adipose tissue (VAT) volume measurements between methods with BIA systematically overestimating VAT compared to DXA. WC was more strongly correlated with DXA FM (rho = 0.90, p < 0.001) than WHtR (rho = 0.83, p < 0.001). BIA had some agreement with DXA; however, they are not equivalent measures for the range of BMIs explored, with DXA remaining the more informative tool. WC is a useful and simple assessment tool for obesity.