Background/Objectives: Patient positioning during surgery can influence intra- and postoperative complications. Therefore, we assessed the impact of the sitting and park-bench positions on anesthetic parameters and complications in neurosurgical patients. Methods and Patients: For this retrospective study, 314 adults who underwent neurosurgical procedures for posterior fossa pathologies were divided into two groups: sitting (n = 231) and park-bench (n = 83). The following data were collected, monitored, recorded, and compared: age, sex, tumor type, surgical approach, cardiovascular and respiratory complications, and postoperative surgical complications. The association of hypotension with the position was further investigated through multivariate logistic regression models by adjusting for CO2 decrease, desaturation, and documented gas embolism. Results: The average age was significantly lower in the sitting group (55 years, interquartile range (IQR) = 43–63; female proportion = 59.74%) than in the park-bench group (62 years, IQR = 45–74; female proportion = 57.83%) (p < 0.001). Cerebellopontine angle tumors were detected in 37.23% of the patients who underwent an operation in the sitting position and in 7.26% who underwent an operation in the park-bench position (p < 0.001). Patients in the sitting position had significantly greater anesthetic complication (91.77% vs. 71.08%, p < 0.001), hypotension (61.9% vs. 16.87%), and >2 mmHg CO2 decrease (35.06% vs. 15.66%, p < 0.001) incidences. Hypoxemia and death occurred more frequently in the park-bench group (8.43% vs. 1.73% and 6.03% vs. 1.3%, respectively). Conclusions: Compared with the park-bench position, the sitting position was associated with a greater specific anesthetic complication incidence and lower postoperative mortality rate, indicating a need for careful risk-benefit assessment when selecting each individual patient’s surgical position.