Background: Herpes zoster (HZ) is often accompanied by severe neuropathic pain, known as herpes zoster–related pain (ZAP), which greatly impairs patients’ quality of life. Hyaluronic acid (HA) possesses anti-inflammatory and neuroprotective properties. Previous studies have shown that subcutaneous injection of 35 kDa HA fragments can rapidly relieve various types of pain, including ZAP. This study aimed to evaluate the analgesic efficacy of a 10% high-concentration 35 kDa HA fragment (HA35) gel applied topically in patients with ZAP. Methods: Four patients with ZAP (aged 57–77 years) were included. All received topical application of 10% HA35 gel; one patient additionally used a skin protective film to prevent gel drying. Pain intensity was assessed using the Numeric Rating Scale (NRS, 0–10) before and after treatment. Results: In three patients with acute ZAP, the mean NRS score decreased by approximately 55% within 2 minutes after application and dropped to 1–2 after 20 minutes, with analgesic effects lasting about 4 hours. In one patient with postherpetic neuralgia (PHN), the combination of HA35 gel and skin protective film extended the analgesic duration beyond 8 hours and significantly reduced erythema and swelling. Conclusions: The 10% high-concentration HA35 gel provided rapid and safe analgesia in ZAP, and the addition of a skin protective film further prolonged the duration of pain relief. This non-invasive, simple, and well-tolerated method offers a promising new topical approach for managing ZAP.