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To well address the problem of low stability for Ru-based catalysts against sintering and leaching during synthesis and aqueous levulinic acid (LA) hydrogenation to γ-valerolactone (GVL), herein we demonstrate an "inside-to-outside" synthetic strategy for robust yolk-structured nanospheres within a single Ru nanoparticle (NP, 4.2 nm) anchored inside the mesoporous shell (pore size, 4.0 nm), denoted as YS Ru@HMCS (yolk-structured Ru encapsulated into hollow mesoporous carbon sphere). Such a shell-supported-core configuration combines the