A green, simple, and effective method for the extraction of sugarcane lipids from sugarcane rind was investigated by response surface methodology. The optimum conditions of technological progress obtained through response surface methodology were as follows: liquid-to-solid ratio 7.94: 1 mL/g, extraction temperature 50°C and extraction time 5.98 h. The practical sugarcane lipids extraction yield was 6.55 ± 0.28%, which was in good consistence with the predicted extraction yield of 6.47%. The results showed that the sugarcane lipids extraction yield obtained in optimum conditions increased by 1.16∼7.28-fold compared to the yields obtained in single-factor experiments. After saponification and SPE steps, the nonsaponifiable fraction of sugarcane lipids was analyzed by gas chromatography with mass spectrometry and high-performance liquid chromatography. β-Sitosterol, stigmasterol, and campesterol were the prevailing phytosterols in the sample, while fucosterol, gramisterol, stigmast-7-en-3-ol, (3β,5α,24S)-, stigmasta-4,6,22-trien-3α-ol, and cholest-8(14)-en-3β-ol acetate were also identified as minor steroids. Furthermore, the content of β-sitosterol and a mixture of campesterol and stigmasterol (quantified by high-performance liquid chromatography) was 44.18 mg/100 g dry weight and 43.20 mg stigmasterol/100 g dry weight, respectively. Our results indicate that sugarcane rind is a good source of phytosterol.