The specific heat of undercooled liquid Ni80Fe10Cu10 alloy was experimentally measured by electromagnetic levitation drop calorimeter, and also numerically simulated by the molecular dynamics method. The achieved maximum undercooling is up to 252 K (0.15 TL) in the experiments, and the measured result is 41.67 J mol−1 K−1. The simulation provides calculated data within 0∼702 K undercooling range, which is much broader than the experimental regime. The simulated value is 37.02 J mol−1 K−1. Although there exists a difference of 4.65 J mol−1 K−1 between them, the result is quite acceptable for simulation. Furthermore, the liquid structure of undercooled Ni80Fe10Cu10 alloy is studied in terms of the total and partial pair distribution functions, which display that the ordered degree of atoms enhances from a normal liquid to metastable state.