Background: Aneurysmal subarachnoid hemorrhage (aSAH) is an acute neurosurgical emergency with a significant fatality rate. In addition to acute brain injury, a considerable part of patients suffering from aSAH develops secondary brain damage such as cerebral vasospasm (CVS). CVS exacerbates the mortality. Therefore, it is urgently needed to find a biomarker, which could predict secondary brain and lead to operation by physicians more promptly. S100B, produced and released by astrocytes, has proven to be an important biomarker for brain injury. Methods: In this present study, 51 patients with aSAH were included. Five CSF samples from each patient were obtained via lumbar puncture and were detected using electrochemiluminescence immunoassay (ECLIA). Results: It indicated that S100B had a higher concentration in CSF of patients treated by surgical clipping after aSAH than that treated with endovascular coiling. In addition, the mean CSF S100B level in patients without CVS was much lower compared with patients with CVS. And, the expression of S100B increased along with the Fisher Grade at the same day after aSAH attacked and decreased as time went on. Moreover, the CSF S100B level of different time points and the mean CSF S100B level can predict the risk of CVS. Conclusions: These data suggest that CSF S100B can be served as a predictor of CVS, which triggers an immediate management by clinicians to prevent secondary exacerbation.