Valentine made Maitland pay heavily for a turnover coming out of defence to claim a first-half winner at the Maitland Sportsground on Saturday.
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Valentine wrested control of the ball just inside their attacking half and were able to find striker Nicholas Martinelli unmarked.
Martinelli unleashed a vicious strike from 30 metres out in the middle of the park beating a lunging Maitland keeper Taylor Pate to his left just on 25 minutes.
The strike was against the run of play for the first 20 minutes, but despite Maitland spending most of that time in attack they were unable to break down the resolute Valentine defence.
The chances they did create they were unable to take advantage of and the one time Valentine keeper Brodie Volklene was beaten the ball was cleared off the line by the defence.
His Maitland counterpart Pate had a tremendous game and pulled of a couple of terrific saves which prevented Valentine from adding to their lead.
Maitland worked hard but lacked cohesion in their movement into the front third and the wall of Valentine orange shirts blunted their attacks while always looking dangerous on the counter.
Charlie Cox was the Magpies' best. He worked himself into the ground and looked the most likely to provide the pass to unlock the Valentine defence.
Magpies coach Mick Bolch said the Magpies had to do a lot better with the ball going forward.
"They are set up very well defensively and catch you on transition," he said of Valentine.
"It was a poor turnover from us in the middle of the park and two quick passes and good finish by the boy gave them the lead.
"We need to do better, I don't know if we had any shots on target ourselves so we weren't creating a great deal.
"I thought Taylor (Pate) was really good and I thought Charlie Cox in the middle was really good. He won a lot of the ball.
"Overall we've got a lot to improve on."
The Magpies have the El-Clasicoal derby next week against Weston at Rockwell Automation Park.
The Bears opening game against Edgeworth was postponed with a washout.
Maitland's NPL women's opening round game against Newcastle Olympic was also postponed because of a washout.