It is the 23-year-old's second overseas stint and first in Europe, after spending the 2019 season at NWSL club Washington Spirit.
Harrison will head to Eindhoven when the Eredivisie resumes, in preparation for the 2020-21 season. The 2019-20 competition is suspended until at least June 1, with PSV seven points clear on top.
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"I'm obviously super excited," Harrison told the Matildas' website.
"I guess it's a little strange at the moment being so excited. However, when that green light does come, and I can get there, it's just exciting thinking about it all."
A versatile midfielder who can also play at full-back, Harrison -- who has previously returned from two ACL injuries -- enjoyed an excellent W-League season at Western Sydney Wanderers.
Harrison was part of the Matildas' squad at the 2019 Women's World Cup, making an appearance as a substitute in the round of 16 loss to Norway.
But she was not included in the squad for Australia's recent Olympic qualifiers, and hoped strong form overseas would put her back in contention.
"A lot of progress is made on the field and playing consistent minutes," Harrison said.
"For me being a longer season in Europe, and a competitive season over there with a lot of games, I think is exactly what I need right now.
"From that hopefully more opportunities come from a national team perspective."