Valentine have lost star recruit Adam Hughes before getting him on the field after the former Perth and Adelaide A-League player took up a coaching opportunity in the Chinese third division.
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The 37-year-old midfielder or defender was a standout for Charlestown in 2019 after joining the Northern NSW NPL side mid-season following a professional career spanning 18 years.
He linked with Valentine as a player and assistant coach for 2020 but he informed the club on Monday that he had been offered the head coaching role with Jilin Baijia FC in China League Two.
He played for Zhejiang Yiteng in China between 2012-18 before returning to the Hunter, where he started his career at Newcastle.
Valentine co-coach Darren Sills said Hughes was contacted by Jilin Baijia about the role and he travelled to China over the weekend.
Sills told his squad about the loss on Tuesday.
"It was a rushed thing but it was too good an opportunity for him to turn down," Sills said. "He wants to return to professional football as a coach and from the couple of sessions he put on for us, I think he will make an excellent one."
Sills said the club were now looking for a centre-back to replace Hughes.
Meanwhile, Spaniard Fortia Munts has arrived in Australia and will start training with Valentine next week. Munts, Alex Read (Maitland), Danny Ireland (Charlestown) and Dain Greentree (Jaffas) are additions for Phoenix this year.