The Union Inn was built by George Muir. George Muir died in December 1833 and his wife Elizabeth took out a license for The Family Hotel in East Maitland in 1834.
James Pawsey held the license for the Union in 1833-34. Had previously been innkeeper at the Australian Inn in Newcastle. His wife Dorothy died at the Australian Inn in 1832.
In November 1833 the premises of the Union Hotel and 14 other buildings allotments were advertised for sale. The hotel had a frontage of 68 feet in Newcastle Street East Maitland and 256 feet on a street and road leading to Green Hills. A road 12 feet wide from Newcastle Street to communicate with the Stable yard had been made. In the house there were 2 rooms 30 ft by 20 ft, a hall 14 ft by 20 ft.; 8 good bed rooms, a bar with accommodations for a family, a large kitchen and store, also a well of water. James Pawsey had taken a lease on the hotel for three years.
According to the following article James Cox had been publican at the Union Inn for several years by 1844.......
Quit Rent sale - A sale of Mr. James Cox's furniture for arrears of quit rent, took place at his Hotel East Maitland 25 October. The sum levied for was £140 which had been allowed to accumulate for the last ten or twelve years. The furniture in every room of the house was sold, and though there was a large number of persons present at the sale such was the feeling evinced that scarcely any person was found to bid; the property which was sold cost originally between £800 and £900 and it was sold for £34; for instance two beds and bedroom furniture were knocked down for £1/3- shillings. This sale must, we think, clearly show the folly and injustice of the government in enforcing the collection of these quit rents at the present time. It is evident that parties will not bid at such sales, and whatever is sold is disposed of at a most ruinous sacrifice, and with great injustice towards the party levied upon, without realising after all the amount levied. 
William Slack was Innkeeper in 1845 having previous kept the Shamrock Inn. He left the Union Inn for the Rose Inn in 1846 
In April 1846 The Union Inn was advertised for lease for a term of years on 'very reasonable terms' and with a promise that should an offer be made by any respectable party the premises would be put into thorough repair.