Real-time detection of early chatter is a vital strategy to improve machining quality and material removal rate in the high-speed milling processes. This paper proposes a maximum entropy (MaxEnt) feature-based reliability model method for real-time detection of early chatter based on multiple sampling per revolution (MSPR) technique and second-order reliability method (SORM). To enhance the detection reliability, the MSPR is used to acquire multiple sets of once-per-revolution sampled data (i.e., MSPR data) and to overcome the shortcoming of the once-per-revolution sampling. The proposed MaxEnt feature-based reliability model method solves the issue of the real-time detection of early chatter while ensuring its reliability. The failure hazard function (FHF) is estimated as a chatter indicator by using the SORM with the MaxEnt feature. The proposed method consists of five steps. First, set the prior parameters. Then collect data by using the MSPR technique. Next, calculate a set of the standard deviation of the data collected as a chatter feature and estimate the chatter indicator FHF by applying the SORM with the MaxEnt feature. Finally, implement the real-time detection of early chatter based on the estimated chatter indicator FHF and the threshold FHF0. The proposed method is applied to the high-speed milling process. Two examples prove that the proposed method can detect two kinds of early chatter: the early-stage of a severe chatter and the slightly intolerable chatter.