Objective We aimed to assess the success rate of the GreenLight laser photoselective vaporization of the prostate (GLL PVP) procedure for enlarged prostates in patients with and without preoperative long-term catheters. Methodology A retrospective data analysis was conducted on 46 patients. Data were collected from clinical health records and radiology images. The parameters studied in this analysis included the patient's age, prostate volume, medical management before surgery, and whether the patient had a catheter or not prior to the surgery. Results A total of 46 GLL PVP surgeries were performed over a 12-month period from May 2023 to May 2024 at West Middlesex University Hospital in London. Patients had a mean age of 73.2 ± 8.12 years, and their prostate volume was 57.7 ± 25.96 cc. Before the surgery, 14 cases (30%) were using long-term catheters, and 32 cases (70%) were not. Additionally, 40 cases (87%) were receiving medical management for lower urinary tract symptoms (LUTS). After the surgery, 39 cases (85%) passed their first trial without catheter (TWOC), and seven cases (15%) failed it, regardless of whether they had used catheters before the surgery. Patients using long-term catheters before the operation had a 71% success rate in passing their first TWOC and a 29% failure rate. Conclusion Our study found that GLL PVP has a significant positive impact on elderly individuals with a large prostate volume, regardless of whether they had long-term catheters or not prior to the operation. Additionally, our findings indicate that patients without preoperative long-term catheters experience significantly better outcomes.