He was consecrated on June 25, 1780, by Cardinal Bernardino Giraud.

Vincenzo Labini was an intimate friend of St Alphonsus Maria de' Liguori the Bishop of St Agata dei Goti and founder of the Redemptorists.

Some of the changes that Labini brought in Malta were that the procession of St Gregory was transferred from March 12 to the Wednesday after Easter, he ordered daily Sacramental Benediction in all parish churches and that bells must be rung every Thursday, an hour after sunset, in memory of the institution of the Eucharist.

Labni led the diocese under three different occupants: the Knights, the French and the British.

Archbishop Labini died on April 30, 1807, and was buried in the Cathedral at Mdina.