The purpose of this study was twofold: 1) compare body volume (BV) estimated from dual energy X-ray absorptiometry (DXA) to BV from a criterion underwater weighing (UWW) with simultaneous residual lung volume (RLV), and 2) compare four-compartment (4C) model body fat percentage (BF%) values when deriving BV via DXA (4C_DXA) and UWW (4C_UWW) in physically active men and women. One hundred twenty-two adults (62 men and 60 women) who self-reported physical activity levels of at least 1,000 MET·min·wk^-1 volunteered to participate (age = 22 ± 5 years). DXA BV was determined with the recent equation from Smith-Ryan et al. while criterion BV was determined from UWW with simultaneous RLV. The mean BV values for DXA were not significant compared with UWW in women (p = .80; constant error [CE] = 0.0L), but were significantly higher in the entire sample and men (both p < .05; CE = 0.3 and 0.7L, respectively). The mean BF% values for 4C_DXA were not significant for women (p = .56; CE = –0.3%), but were significantly higher in the entire sample and men (both p < .05; CE = 0.9 and 2.0%, respectively). The standard error of estimate (SEE) ranged from 0.6–1.2L and 3.9–4.2% for BV and BF%, respectively, while the 95% limits of agreement (LOA) ranged from ±1.8–2.5L for BV and ±7.9–8.2% for BF%. 4C_DXA can be used for determining group mean BF% in physically active men and women. However, due to the SEEs and 95% LOAs, the current study recommends using UWW with simultaneous RLV for BV in a criterion 4C model when high individual accuracy is desired.