Introduction, objectives: Obesity is a global health problem with a great negative impact on health. Among the pathologies caused by obesity are insulin resistance and metabolic syndrome, which constitute an increasingly common health problem in both developed and developing countries. The aim of this study was to examine the relationship between two scales that assess obesity—based on hip circumference—and metabolic syndrome (MetS) and insulin resistance risk scales as predictors of these alterations. Materials, methods: A descriptive, cross-sectional study was carried out on 193,462 workers from different Spanish regions and work groups between January 2019 and September 2021. Abdominal volume index (AVI) and body adiposity index (BAI) were evaluated to assess obesity and its association with insulin resistance using three risk scales (TyG index, Triglycerides/HDL, and METS-IR), while their association with metabolic syndrome was determined using the NCEP ATP III, IDF, and JIS models. Results: The results of the ROC curves to determine the predictive value of BAI and AVI in relation to the three criteria evaluated to calculate MetS in all instances presented a higher area under the curve (AUC) for AVI. The high values of AVI stand out for predicting MetS when applying the IDF criteria. The cut-off point in women was 13.70 with a Youden index of 0.802, whereas in men, the cut-off point was set at 17.59 with a Youden index of 0.672. Regarding the relationship of BAI and AVI with insulin resistance risk scales for both sexes, the AUC only revealed high values when using the METS-IR formula for both AVI and BAI. The AVI cut-off points to predict high values of insulin resistance risk scales in women were established at 13.12 with a Youden index of 0.722. In men, the cut-off point was 17.59, with a Youden index of 0.626. The BAI cut-off points in women were set at 33.88 with a Youden index of 0.748. In men, the cut-off point was 27.91, with a Youden index of 0.598. Conclusions: AVI demonstrated its value as a predictor of metabolic syndrome while exclusively applying the IDF criteria. AVI and BAI demonstrated their value as predictors of high values of insulin resistance risk scales only in the case of METS-IR. This predictive value is also higher in women.