PurposeDevelop a novel 2D cardiac MR fingerprinting (MRF) approach to enable simultaneous T1, T2, T2*, and fat fraction (FF) myocardial tissue characterization in a single breath‐hold scan.MethodsSimultaneous, co‐registered, multi‐parametric mapping of T1, T2, and FF has been recently achieved with cardiac MRF. Here, we further incorporate T2* quantification within this approach, enabling simultaneous T1, T2, T2*, and FF myocardial tissue characterization in a single breath‐hold scan. T2* quantification is achieved with an eight‐echo readout that requires a long cardiac acquisition window. A novel low‐rank motion‐corrected (LRMC) reconstruction is exploited to correct for cardiac motion within the long acquisition window. The proposed T1/T2/T2*/FF cardiac MRF was evaluated in phantom and in 10 healthy subjects in comparison to conventional mapping techniques.ResultsThe proposed approach achieved high quality parametric mapping of T1, T2, T2*, and FF with corresponding normalized RMS error (RMSE) T1 = 5.9%, T2 = 9.6% (T2 values <100 ms), T2* = 3.3% (T2* values <100 ms), and FF = 0.8% observed in phantom scans. In vivo, the proposed approach produced higher left‐ventricular myocardial T1 values than MOLLI (1148 vs 1056 ms), lower T2 values than T2‐GraSE (42.8 vs 50.6 ms), lower T2* values than eight‐echo gradient echo (GRE) (35.0 vs 39.4 ms), and higher FF values than six‐echo GRE (0.8 vs 0.3 %) reference techniques. The proposed approach achieved considerable reduction in motion artifacts compared to cardiac MRF without motion correction, improved spatial uniformity, and statistically higher apparent precision relative to conventional mapping for all parameters.ConclusionThe proposed cardiac MRF approach enables simultaneous, co‐registered mapping of T1, T2, T2*, and FF in a single breath‐hold for comprehensive myocardial tissue characterization, achieving higher apparent precision than conventional methods.