Electrochemical detection of metal cations at paper-based sensors has been suggested as an attractive alternative to current spectroscopic and chromatographic detection techniques due to the ease of fabrication, disposable nature, and low cost. Herein, a novel carbon black (CB), dimethylglyoxime (DMG) ink is designed as an electrode modifier in conjunction with 3-electrode inkjet-printed paper substrates for use in the adsorptive stripping voltammetric electroanalysis of nickel cations in water samples. The developed method provides a novel, low-cost, rapid, and portable adsorptive stripping detection approach towards metal analysis in the absence of the commonly used toxic metallic films. The study demonstrated a novel approach to nickel detection at paper-based sensors and builds on previous work in the field of paper-based metal analysis by limiting the use of toxic metal films. The device sensitivity is improved by increasing the active surface area, electron transfer kinetics, and catalytic effects associated with non-conductive dimethylglyoxime films through CB nanoparticles for the first time and confirmed by electroanalysis. The first use of the CB-DMG ink allows for the selective preconcentration of analyte at the electrode surface without the use of toxic Mercury or Bismuth metallic films. Compared to similarly reported paper-based sensors, improved limits of detection (48 µg L-1), selectivity, and intermetallic interferences were achieved. The method was applied to the detection of nickel in water samples well below World Health Organization (WHO) standards.