[2] On 2 February 2023, Munro was consecrated a bishop by Justin Welby at Canterbury Cathedral during the same service as Jane Mainwaring and Martin Gainsborough.

[5] As of October 2024, Munro is an honorary assistant bishop in 10 dioceses: Blackburn, Sheffield, London, Oxford, Chelmsford, Chester, Durham, Southwark, Peterborough and Bath and Wells.

[9] Munro came into office as the General Synod was discussing Anglican bishops' approval (through the Living in Love and Faith process) of same-sex blessings in the Church of England and revisiting the restrictions imposed on gay clergy in same-sex marriages or civil partnerships.

[10] Munro commented that the General Synod debate: "could threaten to break our unity on the doctrine of marriage, redefine our sanctity with respect to holiness and sexual activity, undermine our catholicity having little obvious regard for the wider Anglican Communion or beyond, and jeopardis[e] our apostolicity with respect to the clear teaching of Scripture.

"[8]In December 2023, following the General Synod vote to commend and the subsequent introduction of prayers and blessings for same-sex relationships, he expressed his "great sorrow" and stated that it was a "serious error" that risks "misleading them about issues of sin and salvation".

[11] In a letter to the clergy under his supervision, Munro strongly recommended against the use of the new prayers, arguing that they have questionable legal status, are a potential confusion of Biblical teachings, and lack clear guidance for conscience; however, he also invited the clergy not to leave the Church of England and offered spiritual advice to those who may need it following the decision.