Nilutamide (NLD) serves as a crucial anti-androgen drug for prostate cancer treatment; however, its elevated presence poses ecological risks. Monitoring NLD in environmental and biological samples is imperative. Layered double hydroxide (LDH) stands out as an intriguing electrocatalyst material, and this study focuses on enhancing its properties by hydrothermally preparing a hydrophobic LDH through co-intercalation of dodecyl sulfate anion in nickel cobalt carbonate hydroxide (NCCH). The catalytic performance is further improved by incorporating multiwall carbon nanotubes (MWCNT) to achieve precision and sensitivity in the electrochemical detection of NLD. The resulting NCCH/MWCNT-based electrochemical sensor demonstrates excellent structural, functional, and morphological characteristics verified by various spectroscopic techniques. Electrochemical analyses reveal impressive results, including a low detection limit (0.001 μM), quantification limit (0.0036 μM), two linear ranges (0.01–59.19 μM and 59.19–537.19 μM), and high sensitivity (3.957 μA μM−1cm−2). The practical utility is confirmed through successful monitoring of NLD in environmental and biological samples with satisfactory recoveries. In conclusion, NCCH/MWCNT emerges as a superior electrode material for the selective detection of NLD, showcasing its potential in environmental monitoring and clinical applications.