We describe a fast and reliable procedure for the efficient extraction of nitrites in cured meat using microwave-assisted heat and report their in situ determination via voltammetry using an anion-exchanger ionene, hexamethyl-p-terphenyl poly(benzimidazolium) (HMT-PMBI), and nitrogen-doped graphite nanoplatelets (NGNPs). Cyclic voltammetry and chronoamperometry were utilized to evaluate the concentration of the redox mediator within the film and apparent diffusion coefficient. To investigate the suitability of the composite material for sensing applications, HMT-PMBI/NGNPs were tested for their detection of nitrite in bacon samples without the need of any pretreatments or dilutions. HMT-PMBI/NGNP coated electrodes showed enhanced sensitivity in the detection of nitrite ions in bacon with a limit of detection (LoD) of 0.64 µM, sensitivity 0.52 µA µM−1 cm−2, and operating in a linear range between 1–300 µM. The results highlight that the determination of nitrites in cured meat using microwave extraction is in good agreement with standard procedures such as the ISO 2918 and the AOAC International 973.31 methods.