Intended for the church, Maitland took leave from England in 1847, travelled to Mexico and then to the Californian goldfields in 1849. He came to New South Wales, and through his connection with the governor-general Sir Charles FitzRoy, Maitland was appointed commissioner of crown lands and police magistrate at Wellington in 1854. He succeeded the explorer W. H. Hovell as commissioner of crown lands at Goulburn in May 1855. He became president of the Goulburn School of Arts and was active in stimulating public discussion. He believed that Australians were in danger of becomng hidebound by 'worn out and cast off traditions' and that they leaned too far 'towards class privileges and class prohibitions'.
Maitland decided to return to England and gave his farewell lecture at the School of Arts, Sydney, on 9 January 1858. In England he devoted his time to writing. His novel The Pilgrim and the Shrine is largely set in Australia. Maitland's later novels were based on mystical themes and the future of society, envisaging Australia as a powerful nation in By and By. Though published anonymously several libraries have attributed the work The Battle of Mordialloc, or, How We Lost Australia (1888) to Edward Maitland.
Maitland contributed to the Spectator and to the Examiner. He helped to found the Theosophical Society of which he became vice-president. With his close friend Mrs Anna Kingsford (q.v.) he started the Hermetic Society in 1884 and after her death he founded the Esoteric Christian Union in 1891. He wrote profusely but was lamented by his literary colleagues as 'a great natural talent gone to waste'.