Pearson plays new head teacher Vaughan Fitzgerald, described by show bosses as “dominant and forward-thinking”.
He’s joined by Nicola Stephenson as partner Allie who takes the reins of the art department.
The couple’s professional veneer is set to be tested when their own children’s warring behaviour threatens to spill into the classroom.
The new arrivals join core cast Laurie Brett, who plays Christine Mulgrew, Melanie Hill, who plays Maggie Budgeon, Angus Deayton as George Windsor and Zoe Lucker as Carol Barry.
Brian Park, Executive Producer of Waterloo Road says: “We’re absolutely thrilled to have such high quality actors like Neil and Nicola on board.
“Neil is one of the country’s most recognised television acting talents and Nicola’s drama credentials speak for themselves.
“This new pairing is going to make quite an impact on the school. We know the viewers are going to love watching them.”
Waterloo Road is made by Shed Productions (a Shed Media company) for the BBC through BBC Scotland.
BBC bosses have already announced that the series will end for good in 2015.