Film cooling has dramatically contributed to the performance improvement of gas turbines, as it is a very effective cooling technique for gas turbines. Large eddy simulation (LES) began to be used in the study of film cooling 20 years ago, and meaningful results have been found, but it has not yet been intensively reviewed. In this review paper, we analyze and introduce about 70 papers published on LES of film cooling over the past 20 years. Numerical instability must be overcome, and realistic inflow must be generated to perform LES of film cooling. This review summarizes how the groups that performed LES of film cooling solved these problems. In film-cooling research, the main topics are improving the film-cooling performance by preventing the lift-off of the injectant and the effect of flow conditions on film cooling. In addition, LES has also been conducted extensively on the above two topics, and this review focuses on them. Finally, turbulence statistics of film-cooling flow obtained from LES are introduced, and future challenges of film-cooling LES are predicted.