Objectives: Intra-operative transcranial Doppler (TCD) is the gold standard for prediction of cerebral hyperperfusion syndrome (CHS) in patients after carotid endarterectomy (CEA) under general anaesthesia. However, post-operative cerebral perfusion patterns may result in a shift in risk assessment for CHS. This is a study of the predictive value of additional post-operative TCD measurements for prediction of CHS after CEA. Methods: This was a retrospective analysis of prospectively collected data in patients undergoing CEA with available intra- and post-operative TCD measurements between 2011 and 2016. The mean blood flow velocity in the middle cerebral artery (MCAVmean) was measured pre-operatively, intra-operatively, and post-operatively at two and 24 h. Intra-operative MCAVmean increase was compared with MCAVmean increase two and 24 h post-operatively in relation to CHS. Cerebral hyperperfusion (CH) was defined as MCAVmean increase ≥ 100%, and CHS as CH with the presence of headache or neurological symptoms. Positive (PPV) and negative predictive values (NPV) of TCD measurements were calculated to predict CHS. Results: Of 257 CEA patients, 25 (9.7%) had CH intra-operatively, 45 (17.5%) 2 h post-operatively, and 34 (13.2%) 24 h post-operatively. Of nine patients (3.5%) who developed CHS, intra-operative CH was diagnosed in two and post-operative CH in eight (after 2 h [n = 5] or after 24 h [n = 6]). This resulted in a PPV of 8%, 11%, and 18%, and a NPV of 97%, 98%, and 99% for intra-operative, 2 h and 24 h post-operative TCD, respectively. Conclusions: TCD measurement of the MCAVmean 24 h after CEA under general anaesthesia is most accurate to identify patients who are not at risk of CHS.