Emotion, as a psychophysiological state, plays an important role in human communications and daily life. Emotion studies related to the physiological signals are recently the subject of many researches. In This study a hybrid feature based approach was proposed to examine affective states. To this effect, Electrocardiogram (ECG) signals of 47 students were recorded using pictorial emotion elicitation paradigm. Affective pictures were selected from the International Affective Picture System and assigned into four different emotion classes. After extracting approximate and detail coefficients of Wavelet Transform (WT / Daubechies 4 at level 8), two measures of the second-order difference plot (CTM and D) were calculated for each wavelet coefficient. Subsequently, Least Squares Support Vector Machine (LS-SVM) was applied to discriminate between affective states and the rest. The statistical analysis indicated that the density of CTM in the rest is distinctive from the emotional categories. In addition, the second-order difference plot measurements at the last level of WT coefficients showed significant differences between the rest and emotion categories. Applying LS-SVM, the maximum classification rate of 80.24 % was reached for discrimination between rest and fear. The results of this study indicate the usefulness of the WT in combination with nonlinear technique in characterizing emotional states.