She has 2 brothers named Phoenix and Spencer. Spencer appeared on an episode of Bunk'd. Even in that episode, Hazel (maybe an accident from her actor, Tessa Netting) addressed that Emma (Peyton's character) and Eric (Spencer's character) look alike.
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Yes, Peyton and Eli have an older brother named Cooper who is married with three children. He is a partner at the energy research firm of Howard Weil, Labouisse and Friedrichs Inc.