Goals from Hector Moreno and Luciano Narsingh sealed victory for the Eredivisie side after Memphis Depay had opened the scoring.
And Smalling felt the Red Devils were punished for not taking their chances when they arrived.
"[Man Utd lacked] that cutting edge in the final third, in that box, to make more of our possession," he told BT Sport. "
"But in the first half they scored from their only chance and we gave it away on the outside of our box and they punished us with their main two chances. It's a very disappointing night.
"We scored a good goal and we couldn't really kick on from that. We've got a lot to learn to make sure that we bounce back on Sunday [against Southampton].
"You can't [take anything for granted]. Whether that's a league game, a cup game, a Champions League game. If you don't take your chances then if the other team take them.
"Tonight we've been well and truly punished."
The game was marred somewhat by a horrific injury to United left-back Luke Shaw, who suffered a double fracture in his leg after being challenged by Moreno.
And Smalling wished his team-mate well, though he admitted he had not seen the incident clearly.
"I didn't see it. A few of the players did witness it and it was a very sad time. We wish him a quick recovery.
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