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Objectives Among the multimodal non-opioid analgesics for postoperative pain in breast surgery, dexamethasone (Dex) is a well-established drug. It has been tested in various nerve blocks in both perineural (PN) and intravenous routes but is still unexplored in the pectoral nerve (PEC) block. In the current study, we planned to compare perineural dexamethasone (PN-Dex) and intravenous Dex in the PEC block in patients undergoing breast surgery.Design Randomised controlled trial.Setting Tertiary care hospital.Participants 70 American Society of Anesthesiologists grade I and II female patients aged 18–65 years, scheduled to undergo modified radical mastectomy under general anaesthesia.Interventions The patients were allocated into two groups (n=35). Group ID received a PEC block with 30 mL of 0.25% ropivacaine plus 10 mL of normal saline and 8 mg of Dex (5 mL) intravenously. Group PD received a PEC block with 30 mL of 0.25% ropivacaine plus 8 mg of Dex, diluted to 10 mL of normal saline and 5 mL of normal saline, intravenously.Main outcome measures Postoperative pain was assessed using the Visual Analogue Scale. The duration of analgesia and total analgesic consumption were also noted over a 24-hour period.Results The mean duration of analgesia was prolonged in Group PD as compared to Group ID (629.31±40.62 min in Group PD and 430.40±41.28 min in Group ID) (p=0.001). Total analgesic consumption in the first 24 hours postoperatively was also lower in Group PD (87.57±24.21 mg) as compared to Group ID (98.57±35.33 mg).Conclusions PN-Dex 8 mg as an adjuvant to 0.25% ropivacaine for a PEC block is an effective analgesic as compared to intravenous 8 mg Dex along with 0.25% ropivacaine for a PEC block.Registration The study was registered under Clinical Trial Registry-India (CTRI/2021/08/036058).