We obtain for the first time all quadratic-in-spin interactions in spinning binaries at the third subleading order in post-Newtonian (PN) gravity, and provide their observable binding energies and their gauge-invariant relations to the angular momentum. Our results are valid for generic compact objects, orbits, and spin orientations, and enter at the fifth PN order for maximally-rotating objects, thus pushing the state of the art. This is accomplished through an extension of the effective field theory of spinning gravitating objects, and of its computational application. We also discover a new finite-size effect which is unique to spinning objects, with a new "Spin Love number" as its characteristic coefficient, that is a new probe for gravity and QCD. (C) 2022 The Author(s). Published by Elsevier B.V.