Background: specific bioelectrical impedance vector analysis (BIVA) has been proposed as an alternative bioimpedance method for evaluating body composition. This investigation aimed to verify the ability of specific BIVA in identifying changes in fat mass after a 16-week lifestyle program in former athletes. Methods: The 94 participants included in the Champ4life project (clinicaltrials.gov: NCT03031951) were randomized into intervention (n = 49) and control (n = 45) groups, from which 82 athletes completed the intervention (age 43.9 ± 9.2 y; body mass index 31.1 ± 4.6 kg/m2). Fat mass was estimated by dual-energy X-ray absorptiometry. Bioelectric resistance, reactance, phase angle, and vector length were assessed by bioelectric impedance spectroscopy, and the BIVA procedure was applied. Results: A significant (p < 0.05) group x time interaction for fat mass, specific resistance, reactance, and vector length was found. Fat mass and vector length significantly (p < 0.05) decreased in the intervention group, while no change was measured in the control group. Considering the participants as a whole group, changes in vector length were associated with changes in fat mass percentage (r2 = 0.246; β = 0.33; p < 0.001) even after adjusting for age, sex, and group (R2 = 0.373; β = 0.23; p = 0.002). Conclusions: The specific BIVA approach is suitable to track fat mass changes during an intervention program aimed to reduce body fat in former athletes.