In this paper, we use localization algebras to study higher rho invariants of closed spin manifolds with positive scalar curvature metrics. The higher rho invariant is a secondary invariant and is closely related to positive scalar curvature problems. The main result of the paper connects the higher index of the Dirac operator on a spin manifold with boundary to the higher rho invariant of the Dirac operator on the boundary, where the boundary is endowed with a positive scalar curvature metric. Our result extends a theorem of Piazza and Schick [27, Theorem 1.17]. 2014 Elsevier Inc.