The 31-year-old German, who was appointed in June, is the youngest-ever permanent manager of a Premier League team - nearly half the age of the 59-year-old Postecoglou.
Huerzeler, who has impressed so far, will be hoping to put some of his insider knowledge to use on Sunday when Brighton host a Tottenham team one place above his side in the Premier League.
"He spent a day with us last year," Tottenham boss Postecoglou said. "He asked a lot of questions, I gave him too many answers, for sure. I actually palmed him off at one stage because he was asking too many (questions), so I passed him to the other coaches.
"He was inquisitive about everything. He was already a senior manager (in Germany), doing a good job, and the fact that he still wanted to ask questions... he made a real impression on everyone."
Postecoglou was asked whether he would have extended the invitation to Tottenham's training ground had he known that Huerzeler would be a rival this season. "Yes, mate, I would've done," he said. "There's nothing wrong with being a nice person.
"If somebody comes and knocks on your door and wants a cup of tea as a kindred spirit you let him in your house mate. He's not going to take the furniture or steal the cutlery. You kind of trust that."
Postecoglou also praised close-season signing Dominic Solanke following the former Bournemouth forward's recall to the England squad seven years after his sole international appearance.
"Dom's had to work awfully hard in his career," he said. "It's a salient point for all young players that the (career) trajectory doesn't always go linearly. He started at big clubs, was a youth international, made an impact but for one reason or another, didn't get started."
Postecoglou said captain Son Heung-min is unlikely to be available for the trip to the south coast. The South Korea international, substituted with a hamstring injury during Tottenham's Europa League clash with Qarabag last week, missed their victories over Manchester United and Ferencvaros.