In this paper, laser induced human serum Raman spectra of liver cancer are measured. The differences in serum spectra between normal people and liver cancer patients are analyzed. For the typical spectrum of normal serum, there are three sharp Raman peaks and relative intensity of Raman peaks excited by 514.5 nm is higher than that excited by 488.0 nm. However, for the Raman spectrum of liver cancer serum there are no peaks or very weak Raman peaks at the same positions. To liver cirrhosis, the shape of Raman peak is similar to normal and fluorescence spectrum is similar to that of liver cancer from statistic data. Moreover, the liver fibrosis and liver cirrhosis were studied using the technology of laser-induced fluorescence (LIF). The experiment indicates that the blue shift of fluorescence peak differences between the normal, liver fibrosis and liver cirrhosis were observed. These results have important reference values to explore the method of laser spectrum diagnosis.