The selective quantitation of Cr(VI) was developed through colorimetric detection using starch-stabilized silver nanoparticles (starch-AgNPs). The detection of Cr(VI) was based on oxidative degradation of starch-AgNPs as the reduction of UV-Vis signal and the distinctive color change from yellow to colorless of starch-AgNPs were observed. To achieve the highest sensitivity by this method, pH 3, and only 1 min were required for the determination of Cr(VI). For analytical performances, two linear ranges of 0–6 µM and 10–80 µM with limit of detection of 0.93 µM (48 µg/L) and 11.57 µM (0.60 mg/L) were obtained, respectively. The developed colorimetric method was combined with inductively coupled plasma optical emission spectroscopy (ICP-OES) for the speciation analysis of chromium. The concentration of Cr(III) was calculated by subtraction of Cr(VI) from the total chromium concentration determined by ICP-OES. A satisfactory accuracy and precision based on the AOAC guidelines also proved that this simple and rapid sensor was successfully applied for speciation of chromium in real water samples.