A cellulose-based solid amine adsorbent (MCC/TEPAA) with high amino density for the detection and removal of Cr(VI) was designed and prepared through using epichlorohydrin cross-linking with MCC (microcrystalline cellulose) and tetraethylenepentamine (TEPA). The structure and amino density of the cellulose-based solid amine adsorbents could be tailored by adjusting the structure of the amines (triethylenetetramine or diethylenetriamine). The as-prepared cellulose-based solid amine adsorbents could detect and completely remove Cr(VI) from water, and the concentration of Cr(VI) solution after adsorption met the standard concentration of Cr(VI) solution for drinking water (0.05 mg/L). In particular, the MCC/TEPAA, supported by MCC with porosity as a framework, promoted the adsorption rate (adsorption equilibrium within only 10 min), removal rate (100%) of Cr(VI), and adsorption capacity (327.72 mg/g). In addition, the limit of colorimetric detection of Cr(VI) by MCC/TEPAA was 0.5 mg/L at 20 min when other interfering heavy metal ions exist. The adsorption and colorimetric detection mechanism of Cr(VI) on MCC/TEPAA was proposed to include electrostatic interactions, chelating reactions, and oxidation-reduction reactions, all of which contributed to the excellent adsorption and detection performance.