Pavlyuchenkova first made headlines in 2006 by winning the Australian Open junior title, defeating Caroline Wozniacki in the final. She reached another junior Grand Slam final at the French Open where she lost to Agnieszka Radwańska. She then won the US Open junior title by beating Tamira Paszek in the final. Her successful career as a junior also saw her reach the World No. 1 ranking on 30 January 2006. She accumulated an overall win-loss of record of 131–23 and 87–22 in singles and doubles respectively. Her success in juniors enabled her to enter ITF and WTA tournaments, winning an ITF event in Italy in May 2006. Five months later, Pavlyuchenkova received a wildcard into her maiden WTA main-draw appearance at the Kremlin Cup. She lost in the first round to rising Czech Nicole Vaidišová in straight sets.