Purpose This study explores the possibility of using a gradient moment balanced sequence with a quadratically varied RF excitation phase in the magnetic resonance fingerprinting (MRF) framework to quantify T2* in addition to δf, T1, and T2 tissue properties. Methods The proposed quadratic RF phase‐based MRF method (qRF‐MRF) combined a varied RF excitation phase with the existing balanced SSFP (bSSFP)‐based MRF method to generate signals that were uniquely sensitive to δf, T1, T2, as well as the distribution width of intravoxel frequency dispersion, normalΓ. A dictionary, generated through Bloch simulation, containing possible signal evolutions within the physiological range of δf, T1, T2, and normalΓ, was used to perform parameter estimation. The estimated T2 and normalΓ were subsequently used to estimate T2*. The proposed method was evaluated in phantom experiments and healthy volunteers (N = 5). Results The T1 and T2 values from the phantom by qRF‐MRF demonstrated good agreement with values obtained by traditional gold standard methods (r2 = 0.995 and 0.997, respectively; concordance correlation coefficient = 0.978 and 0.995, respectively). The T2* values from the phantom demonstrated good agreement with values obtained through the multi‐echo gradient‐echo method (r2 = 0.972, concordance correlation coefficient = 0.983). In vivo qRF‐MRF‐measured T1, T2, and T2* values were compared with measurements by existing methods and literature values. Conclusion The proposed qRF‐MRF method demonstrated the potential for simultaneous quantification of δf, T1, T2, and T2* tissue properties.