Carbon-alumina composites are prepared for the efficient removal of Cr(VI) from wastewater. Pristine and acid-treated alumina dross (AD and AAD) are copyrolyzed with pine sawdust to form the respective composites, ADPC and AADPC. Excellent absorption properties with Cr(VI) removal efficiency of 95.08% are demonstrated at 60 °C for an initial concentration of 6 μg/mL. The composites combine the merits of char, which provides a high surface-to-volume ratio with abundant functional groups on the surface, and alumina, which provides metal ions for coprecipitation. Carbon structures of pine, char, and composite were analyzed semiquantitatively using 13C NMR by a curve-fitting method. Cr(VI) adsorption is accurately described with chemisorption by the Langmuir isotherm model and a pseudo-second-order kinetic model. The results show that AADPC has more alcohol hydroxyl groups substituted to glucosyl units in amorphous cellulose assigned to the peak at 80 ppm and hemicellulose assigned to peaks at 97 and 101 ppm. Also, it has more phenolic groups in lignin distributed at syringyl units assigned to peaks at 129 and 146 ppm. These oxygen-containing functional groups have a significant influence on Cr(VI) adsorption and reduction to Cr(III) governed by the mechanisms of diffusion, adsorption, complexation, reduction, and coprecipitation. The results of this work provide a new direction for the reuse of biomass and industrial solid wastes to fabricate higher value-added products, i.e., adsorption materials for Cr(VI) removal and stabilization.