<p>Room-temperature spin control in semiconductors is fundamental to spin-optoelectronics. Although inversion symmetry breaking offers one path for spin control in semiconductors, strong spin dephasing at elevated temperatures remains a persistent limitation. Hidden spin polarization without global symmetry breaking provides another promising material design strategy, but robust spin stabilization from this effect has yet to be experimentally realized. Here we show spin stabilization at room temperature in two-dimensional hybrid organic–inorganic perovskites through hidden spin-valley locking. We use functional non-primary ammonium cations to induce symmetry-breaking distortions in the metal-halide layers, producing giant local spin splitting while preserving global inversion symmetry. Time-resolved circular dichroism measurements reveal optically generated spin-polarized carriers that persist for 686 ps in (AzOH)₂PbI₄ and 4.7 ns in the lead-free analogue (AzOH)₂SnI₄ at room temperature, without an external magnetic field. First-principles calculations suggest that these long lifetimes arise from hidden spin valleys, enhanced dielectric screening and reduced spin–orbit-induced scattering in the Sn-based compound. Our design paradigm unlocks inversion-symmetric semiconductors with ultralong spin lifetimes, broadening the materials options for light-driven spin control.</p>