A study was conducted to test the capability of the 14 N nuclear quadrupole resonance (NQR) method to discriminate qualitatively and quantitatively among different forms of piroxicam. Samples of commercial piroxicam form I and its monohydrate were obtained on the local market. Additionally, samples of form I and II were prepared by recrystallization in 1,2-dichloroethane and ethanol, respectively. DSC and FT-IR were employed as reference methods. A 14 N NQR spectrometer was used to measure samples of different forms and mixtures of piroxicam at 2587 and 3439 kHz. DSC and FT-IR clearly confirmed differences between the different piroxicam forms. Measurements of 14 N NQR signals of different forms of piroxicam at 2587 kHz detected only spectral peaks of form I. The dependence of 14 N NQR signal intensity on the concentration of form I in mixtures with the monohydrate showed a clear linear relationship at both measured frequencies, though the scattering of data was greater at 3439 kHz due to the lower S/N ratio. The 14 N NQR method has the potential to become an additional and important spectroscopic tool in the study of solid-state forms, not only of pure active pharmaceutical ingredients or excipients, but also of their mixtures. This ability lends the method to a possible successful utilization at different levels of pharmaceutical manufacturing and product quality control.