St Matthew’s Windsor was established on the frontier with a dual purpose: to bring the civilizing order of the Church of England to a struggling colony, and, in the hearts of its early ministers, to bring the light of the gospel to a challenging environment. Since its foundations, reaching the people of the Hawkesbury with the good news of Jesus has demanded creativity, sacrifice, and passion.
| Tenure | Rector | Notable Contributions |
| 1794–1810 | Rev. Samuel Marsden | 1st Chaplain of the Hawkesbury |
| 1810–1819 | Rev. Robert Cartwright | Served the Windsor district prior to and during the church's initial construction. |
| 1819–1828 | Rev. John Cross | The first to live in the rectory built by William Cox; oversaw the church's consecration. |
| 1828–1829 | Rev. Elijah Smith | |
| 1829–1833 | Rev. Joseph Docker | |
| 1833 | Rev. M. D. Meares | Officiated pro tem (temporarily). |
| 1833–1867 | Rev. Henry Tarlton Stiles | The longest-serving 19th-century rector. |
| 1867–1877 | Rev. Charles F. Garnsey | |
| 1877–1878 | Rev. Henry A. Langley | |
| 1878–1885 | Rev. F. W. Stretton | Established the Vineyard Mission School Church during his tenure. |
| 1885–1890 | Rev. A. R. Blacket | |
| 1890–1893 | Rev. G. D'Arcy Irvine | |
| 1893–1904 | Rev. S. G. Fielding | |
| 1904–1906 | Rev. P. W. Dowe | |
| 1906–1936 | Rev. Norman L. J. Jenkyn | Also served as Mayor of Windsor (1931–1932). |
| 1936–1940 | Rev. G.P Birk | |
| 1940–1947 | Rev. C.L Williams | |
| 1947–1951 | Rev. R.T Hallahan | |
| 1951–1954 | Rev. D.G McGraw | |
| 1954–1960 | Rev. W.F Carter | |
| 1961–1980 | Rev. Canon H Rawson | |
| 1980–1988 | Rev. Canon L.M Abbott | |
| 1988–1999 | Rev. Canon John Butler | |
| 1999–2007 | Rev. Canon Chris Burgess | |
| 2008–2015 | Rev. Aleks Pinter | |
| 2015–2025 | Rev. Chris Jones | Officiated during the Bicentenary of the Church and Rectory |
| 2026– | Rev. Shane Dirks |