Estimating of the depth of anaesthesia (DoA) in operations has always been a challenging issue due to the underlying complexity of the brain mechanisms. Electroencephalogram (EEG) signals are undoubtedly the most widely used signals for measuring the DoA. In this paper, a novel EEG-based index is proposed to evaluate the DoA for 24 patients receiving general anaesthesia with different levels of unconsciousness. Sample Entropy (SampEn) algorithm was in order to acquire the chaotic features of the signals. After calculating the SampEn from the EEG signals, random forest was utilised for developing learning regression models with Bispectral index (BIS) as the target. Correlation coefficient, mean absolute error, and area under the curve (AUC) were used to verify the perioperative performance of the proposed method. Validation comparisons with typical nonstationary signal analysis methods (i.e., recurrence analysis and permutation entropy) and regression methods (i.e., neural network and support vector machine) were conducted. To further verify the accuracy and validity of the proposed methodology, the data is divided into four unconsciousness-level groups on the basis of BIS levels. Subsequently, analysis of variance (ANOVA) was applied to the corresponding index (i.e., regression output). Results indicate that the correlation coefficient has improved to 0.72 ± 0.09 after filtering and to 0.90 ± 0.05 after regression from the initial values of 0.51 ± 0.17. Similarly, the final mean absolute error has dramatically declined to 5.22 ± 2.12. In addition, the ultimate AUC has increased to 0.98 ± 0.02, and the ANOVA analysis indicates that each of the four groups of different anaesthetic levels demonstrated significant difference from the nearest levels.Furthermore, the random forest output was extensively linear in relation to BIS, thus better DoA prediction accuracy. In conclusion, the proposed method provides a concrete basis for monitoring patients' anaesthetic level during surgeries.