Nitazenes are highly potent illicit substances that have increased in use since 2019. As of 2025, there are not many presumptive tests for nitazenes, especially those capable of detecting trace amounts. This research aims to create a new presumptive test based on current changes within an electrochemical system to preliminarily identify nitazenes. Five benzimidazole-based simulants were synthesized to assess electrochemical activity. These structures lacked the opioid receptor activity of nitazenes; however, they contained the same benzimidazole core. This was to investigate whether the main body of the molecules would create an electrochemical response and indicate whether nitazenes could be detected. Once the simulants were synthesized, the samples were combined with 4-aminobenzoic acid (4-ABA) monomer and subjected to electro polymerization through cyclic voltammetry on a modified multi-walled carbon nanotube (MWCNT) screen-printed carbon electrode (SPCE). Multiple parameters for the preparation and performance of the molecularly imprinted (MIP) sensor were assessed and analyzed to determine the most effective detection method. Detection was carried out using square-wave voltammetry to determine the electroactive behavior of the nitazene simulants at both MIP and control non-imprinted (NIP) sensors. This demonstrated the successful imprinting of nitazene simulants onto the electrode. The MIP/MWCNT/SPCE showed a linear relationship between peak current intensity and the concentration of the nitazene simulants in the range of 0.001–100 µg/mL. Simulants containing a nitro-group exhibited increased conductivity, while those lacking a nitro group exhibited decreased conductivity. This trend was corroborated by impedance results obtained in potassium ferricyanide. Selectivity testing with common adulterants showed minimal interference, though aspirin and caffeine were found to increase system conductivity. Overall, the sensors developed in this study successfully detected the synthesized nitazene simulants if they contained the benzimidazole core, and they were also able to detect these simulants in the presence of aspirin, caffeine, and starch.