X-ray fluorescence is a fast, cost-effective, and eco-friendly method for elemental analyses. Portable X-ray fluorescence spectrometers (pXRF) have proven instrumental in detecting metals across diverse matrices, including plants. However, sample preparation and measurement procedures need to be standardized for each instrument. This study examined sample preparation methods and predictive capabilities for nickel (Ni) concentrations in various plants using pXRF, employing empirical calibration based on inductively coupled plasma optical emission spectroscopy (ICP-OES) Ni data. The evaluation involved 300 plant samples of 14 species with variable of Ni accumulation. Various dwell times (30, 60, 90, 120, 300s) and sample masses (0.5, 1.0, 1.5, 2.0g) were tested. Calibration models were developed through empirical and correction factor approaches. The results showed that the use of 1.0g of sample (0.14gcm-2) and a dwell time of 60s for the study conditions were appropriate for detection by pXRF. Ni concentrations determined by ICP-OES were highly correlated (R2 = 0.94) with those measured by the pXRF instrument. Therefore, pXRF can provide reliable detection of Ni in plant samples, avoiding the digestion of samples and reducing the decision-making time in environmental management.