Coal gasification slag (CGS), a massive industrial solid waste, possesses inherent adsorptive potential that remains underutilized due to pore blockage by amorphous siliceous phases. Conventional modification strategies typically rely on energy-intensive high-temperature processes. Herein, we report a facile, low-temperature alkaline activation approach to transform CGS into a high-efficiency adsorbent (denoted NCGS) for Cd²⁺ removal. Sodium hydroxide (NaOH) solution was employed under mild conditions (90 °C) to selectively etch siliceous species, thereby generating a porous architecture and enriching surface oxygen-containing functionalities. Orthogonal experimental design identified optimal synthesis parameters (1 mol/L NaOH, solid–liquid ratio of 1:30 g/mL, 12 h), yielding NCGS with significantly enhanced textural properties. The adsorption isotherm was well described by the Langmuir model, with a maximum capacity of 87.06 mg/g at pH 6.0, while kinetic studies indicated the adsorption process could be described by pseudo-second-order kinetic model. Comprehensive characterization via SEM-EDS, FTIR, and XPS elucidated a multi-mechanistic adsorption pathway mainly involving ion exchange (Na⁺/Cd²⁺) and coordination complexation. Life cycle assessment analysis revealed that NCGS production generates 11.23 kg CO₂ eq emissions, with transportation accounting for 88%. This study presents an energy-saving and environmentally friendly strategy to unlock the adsorptive potential of CGS, providing a highly promising waste-based adsorption material for the remediation of Cd²⁺-contaminated water.