Hoechlin will be making his debut as Clark Kent in the first two episodes of season two, reported Digital Spy.
"Greg Berlanti and I have wanted to work with Tyler for ages, so this worked out perfectly because Tyler is Superman," said executive producer Andrew Kreisberg.
"We are so thrilled and humbled to add another amazing actor to the legacy of this iconic character."
Besides playing Derek Hale in "Teen Wolf" between 2011 and 2014, Hoechlin is known for his roles in "7th Heaven" and Richard Linklater's "Everybody Wants Some!".
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Previously, Superman's presence on Supergirl has been limited to being shot from behind or shown only in flashbacks as a child.
A full-scale appearance from Superman was confirmed by Kreisberg earlier this month.
"Supergirl" will return on The CW this fall.