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Background Postoperative liver failure (PLF) is a serious complication of extended liver surgery. The need for clinical bedside tests to predict sufficient liver function in the remnant liver tissue after surgery and to monitor liver function and its potential for regeneration is vital to increase the safety of patients in the perioperative setting. Methods The liver maximum capacity (LiMAx) test was prospectively applied both preoperatively (n = 40) and postoperatively (n = 19) for 40 patients who underwent extended liver surgery (≥3 segments). LiMAx values were correlated with liver-specific blood parameters as well as with volumetric analysis regarding their potential as predictors of the clinical outcome and for monitoring the liver functional capacity. Results The majority of patients (n = 33; 82.5%) had high preoperative LiMAx values (> 315 µg/kg/h), while only seven patients (17.5%) had medium values (140–315 µg/kg/h), and none of the patients had low values (< 140 µg/kg/h). According to the LiMAx algorithm and preoperative volumetry, expected and measured postoperative LiMAx were compared. They differed in 7 out of 13 patients (53.8%) with a cut-off ≥10%. After surgery, patients with an uneventful recovery (n = 12) showed a typical trend in the LiMAx values, with a drop after surgery followed by an increase until 14 days after surgery. This course was reflected similarly by blood-based tests (e.g., prothrombin time). In patients with postoperative complications, a decrease in LiMAx was associated with a prolonged recovery. Conclusions For patients undergoing extended liver surgery within the 0.5% rule, which is the clinical gold standard, LiMAx values do not offer any additional information. Additionally, LiMAx may reflect liver recovery but it did not deliver additional information regarding postoperative liver recovery. The clinical use of LiMAx might be relevant in selected patients beyond the 0.5% rule.