Background: An adequate early mobilization followed by an effective and pain-free rehabilitation are critical for clinical and functional recovery after hip and proximal femur fracture. A multimodal approach is always recommended so as to reduce the administered dose of analgesics, drug interactions, and possible side effects. Peripheral nerve blocks should always be considered in addition to spinal or general anesthesia to prolong postoperative analgesia. The pericapsular nerve group (PENG) block appears to be a less invasive and more effective analgesia technique compared to other methods. Methods: We conducted multicenter retrospective clinical research, including 98 patients with proximal femur fracture undergoing osteosynthesis surgery within 48 h of occurrence of the fracture. Thirty minutes before performing spinal anesthesia, 49 patients underwent a femoral nerve (FN) block plus a lateral femoral cutaneous nerve (LCFN) block, and the other 49 patients received a PENG block. A non-parametric Wilcoxon–Mann–Whitney (α = 0.05) test was performed to evaluate the difference in resting and dynamic numerical rating scale (NRS) at 30 min, 6 h, 12 h, and 24 h. Results: the PENG block administration was more effective in reducing pain intensity compared to the FN block in association with the LFCN block, as seen in the resting and dynamic NRS at thirty minutes and 12 h follow-up. Conclusion: the PENG block was more effective in reducing pain intensity than the femoral nerve block associated with the lateral femoral cutaneous nerve block in patients with proximal femur fracture undergoing to osteosynthesis.