Untreated tannery wastewater contains a large amount of toxic metals, dyes, and other pollutants, which pose adverse effects on the ecosystem and public health. In this work, a calcium alginate-poly vinyl alcohol-graphene oxide (CA-PVA-GO) composite was prepared to remove metals and dyes, particularly Cr(Ⅲ) and CI acid violet 54 (AV54) dye, from tannery wastewater. FESEM, FTIR, and XRD analyses were applied to characterize the GO and CA-PVA-GO. Different operational variables, viz. pH (3.0–5.5 for Cr(III) and 2–7 for dye), dosage (0.164–2.46 g/L), contact time (10–60 min), initial concentration (39, 65, 98, and 201 ppm for Cr(III) and 21.5, 38.5, 54.5, and 61.75 ppm for dye), and temperature (298, 308, 318, and 328 K) were studied to evaluate the efficiency of the CA-PVA-GO composite. The optimum conditions for Cr(Ⅲ) and AV54 dye adsorption were found to be pH (5.0 and 3.0), dosage (0.82 g/L for both), and time (45 and 60 min), respectively, with 35.35 ± 1.43% and 84.63 ± 2.54% removal efficiency. The experimental data was analyzed through the Langmuir and Freundlich isotherms. The maximum adsorption capacity (qm) was observed at 173.01 and 74.68 mg/g for Cr(Ⅲ) and AV54 dye, respectively. The pseudo-second-order kinetic model was fitted better (R2 = 0.981, 0.995, 0.92, and 0.995) than first-order for AV54 dye adsorption. Thermodynamic analyses revealed that the Cr(Ⅲ) and AV54 dye adsorption processes were spontaneous and exothermic. The value of Gibbs free energy (ΔG) for Cr(III) adsorption was obtained at −7.433, −4.508, −2.626, and −1.311 kJ/mol, whereas it was −5.178, −4.867, −4.628, and −4.555 kJ/mol for dye. The values of ΔH and ΔS were −67.257 and −0.198 kJ/mol for Cr(III) and −10.852 and −0.019 kJ/mol for the dye removal. The regenerated CA-PVA-GO composite was reused successfully. Different physicochemical parameters, viz., concentration, pH, TDS, EC, BOD5, and COD of chrome tanning and dyeing effluents, were analyzed before and after the adsorption. The results of chromium and dye removal from tannery wastewater were 53.18% and 93.91%, revealing that the developed eco-friendly CA-PVA-GO composite could be an operative adsorbent for tannery wastewater treatment and possibly scaled up to an industrial level.