Complex networks have been used intensively to investigate the flow and dynamics of many natural systems including the climate system. Here, we develop a percolation based measure, the order parameter, to study and quantify climate networks. We find that abrupt transitions of the order parameter usually occur ∼1 year before El Niño events, suggesting that they can be used as early warning precursors of El Niño. Using this method, we analyze several reanalysis datasets and show the potential for good forecasting of El Niño. The percolation based order parameter exhibits discontinuous features, indicating a possible relation to the first order phase transition mechanism.