[3] Three years after transferring to the Amsterdam-based club, Van Rhijn began playing for the Ajax B1 team in the youth ranks, winning the national championship under coach Robin Pronk.

On 21 September 2011, Van Rhijn made his debut for the senior squad in a KNVB Cup match against VV Noordwijk, helping his side to a 3–1 away win after coming on as a substitute for Toby Alderweireld in the 65th minute.

The match ended in a 4–0 win for Ajax at the Amsterdam Arena, which saw Van Rhijn playing the full 90 minutes in place of Alderweireld, who was sidelined due to an injury.

[8] The following match day would see Van Rhijn receive a red card for a challenge against AZ defender Nick Viergever in a 3–2 away loss, resulting in his suspension for the Klassieker against Feyenoord on 17 August 2013.

[15] Van Rhijn debuted for the under-17 squad under head coach Albert Stuivenberg on 20 September 2007 in a 2–0 loss against Germany at the U17 Four Nations Tournament in the Czech Republic, where he captained his side.

He made a total of 13 appearances for the U17 squad, also competing in the 2008 UEFA European Under-17 Championship in Turkey where he captained the Dutch to the semi-finals, where they lost to the eventual champions Spain.

[18] While initially skipping the under-20 team and going straight to the under-21 selection, he was later called up for one appearance for the U20 side under head coach Adrie Koster on 29 February 2012 in a friendly match against Denmark that ended in a 3–0 win for the Dutch, with Van Rhijn scoring the final goal.

He competed in the qualifications for the 2013 UEFA European Under-21 Championship under head coach Cor Pot, participating in the main tournament in Israel as well, where the Dutch were eliminated in the semi-finals by Italy.

[22] Fellow Dutch international players Stefan de Vrij, Nick Viergever, Bruno Martins Indi and Adam Maher all made their debut for the first team in that same fixture.