The treatment of wastewater always demands eco-friendly and cost-efficient adsorbents. In this paper, spent mushroom waste (SMW) was modified by a cationic surfactant (cetyltrimethylammonium bromide, CTAB) to eliminate toxic dyes. A characterization of adsorbents confirmed that CTAB was successfully embedded into the SMW structure. The spent mushroom waste, modified by CTAB (SMWC), exhibited an excellent adsorption capacity of 249.57 mg·g−1, 338.67 mg·g−1, and 265.01 mg·g−1 for the Direct red 5B (DR5B), Direct blue 71 (DB71), and Reactive black (RB5) dyes, respectively. Batch experiments indicated that the dye adsorption of SMWC depended mainly on pH, dye concentration, temperature, and ionic strength. The adsorption isotherm could be fitted to the Langmuir model and described by the pseudo-second-order kinetic model. The dye adsorption mechanism was dominated mostly by the chemosorption of the dyes and the SMWC surface. Thermodynamic parameters showed that the adsorption was endothermic and spontaneous. SMWC could successfully remove over 90% of dyes from various water samples. This can be considered a feasible waste resource utility, since it meets both the ecological and the economic requirements for auspicious industrial applications.