In this paper we propose an approach of principal component cluster analysis based on Lyapunov exponent spectrum (LES) to analyze the ECG time series. Analysis results of 22 sample-files of ECG from the MIT-BIH database confirmed the validity of our approach. Another technique named improved teacher selecting student (TSS) algorithm is presented to analyze unknown samples by means of some known ones, which is of better accuracy. This technique combines the advantages of both statistical and nonlinear dynamical methods and is shown to be significant to the analysis of nonlinear ECG time series.