Background: The postoperative complication rate is 30–64% among patients undergoing muscle-invasive and recurrent high-risk non-muscle-invasive bladder cancer surgery. Preoperative risky alcohol use increases the risk. The aim was to evaluate the accuracy of markers for identifying preoperative risky alcohol. Methods: Diagnostic test sub-study of a randomized controlled trial (STOP-OP trial), based on a cohort of 94 patients scheduled for major bladder cancer surgery. Identification of risky alcohol use using Timeline Follow Back interviews (TLFB) were compared to the AUDIT–C questionnaire and three biomarkers: carbohydrate-deficient transferrin in plasma (P–CDT), phosphatidyl-ethanol in blood (B–PEth), and ethyl glucuronide in urine (U–EtG). Results: The correlation between TLFB and AUDIT–C was strong (ρ = 0.75), while it was moderate between TLFB and the biomarkers (ρ = 0.55–0.65). Overall, sensitivity ranged from 56 to 82% and specificity from 38 to 100%. B–PEth showed the lowest sensitivity at 56%, but the highest specificity of 100%. All tests had high positive predictive values (79–100%), but low negative predictive values (42–55%). Conclusions: Despite high positive predictive values, negative predictive values were weak compared to TLFB. For now, TLFB interviews seem preferable for preoperative identification of risky alcohol use.