Objective To explore the molecular basis of the characteristics of the serum auto-fluorescent spectrum in patients with ovarian cancer and the changes that might be induced by surgery. Methods Using fluorospectrophotometer and 300nm excitation light,the serum auto-fluorescent spectrum of 84 patients with ovarian cancer before and after the surgery and 30 healthy people were detected. Meanwhile, the serum tumor signs (CEA, CA199 and CA125), hemoglobin and plasma albumin level of all patients with ovarian cancer were detected. Their correlation with the fluorescence spectral characteristic parameters were analyzed. Results Compared with healthy people, the serum auto-fluorescent spectrum in patients with ovarian cancer exhibited purple-shifted position of λ2 peak and red shift in λ4 peak,had higher peak extent inλ1, λ2, λ4 and λ6 peak, and larger peak area of λ1, λ2, λ3, λ4 and λ6. Compared with those in ovarian cancer patients before surgery, the serum auto-fluorescent spectrum in these patients after operation had red shifts in λ1, λ2 and λ3 peak, lower peak extent in λ1, λ2, λ3 and λ4, and smaller peak area in λ1, λ2, λ3,λ4 and λ6 peak. In ovarian cancer patients, the serum level of CEA was positively correlated with the λ2 peak extent and the peak area of λ2 and λ3, while the serum level of CA125 was positively correlated with the peak extent of λ1-λ4 and λ6 and the peak area of λ1-λ3. The serum level of CA199 was negatively correlated with the λ2 position and positively correlated with the peak extent of λ1-λ6 and the peak area ofλ1-λ3 and λ6 in patents with ovarian cancer. Besides, the serum albumin was positively correlated with theλ2 peak position and negatively with the peak extent of λ1-λ6 and the λ1-λ3 peak area, while the level of hemoglobin was positively correlated with λ1 peak position. Conclusions The elevated serum tumor markers and lower albumin (plasma) level lead to the changes of the serum autofluorescence spectra characteristic parametersin in patients with ovarian cancer.These changes can be modestly corrected by surgery.