Colorimetric sensors are a promising technique for the simple screening of water, food, and environmental samples contaminated with interferents, allowing for color changes to be observed with the naked eye or a spectrophotometer. In this study, a colorimetric sensor for the selective detection of hexavalent chromium ion (Cr(VI)) contamination in water was developed. A combination of sodium borohydride-coated gold and citrate-capped silver nanoparticles (Na-AuNPs/cit-AgNPs) was employed as a colorimetric probe. Upon the addition of Cr(VI)-contaminated tap water in the colorimetric probe solution, the color sequentially transitioned from its initial orange to dark reddish-purple, dark purplish-red, dark blue-violet, and gray. This colorimetric strategy relies on AgNP dissolution and AuNP aggregation in the presence of the Cr(VI) ions. The dissolution of AgNPs is evidenced by the reduction of the characteristic peak of AgNPs at 400 nm, while the aggregation of AuNPs leads to a red shift in the absorption band at 514 nm, accompanied by broad absorption in the 500–700 nm range. The limits of detections were found to be 22.9 and 50 ppb using a spectrometer and by visual observation, respectively. The synthesized AuNPs and AgNPs are very stable in the presence of media containing complicated ions. We further demonstrated the practical applicability of the developed system for detecting Cr(VI) in real samples, including natural water and artificial urine, highlighting its potential for addressing Cr(VI) contamination in practical scenarios.