<p>Optically addressable solid-state spins have been extensively studied for quantum technologies, offering unique advantages for quantum computing, communication, and sensing. Advancing these applications is generally limited by finding materials that simultaneously provide lifetime-limited optical and long spin coherences. Here, we introduce ¹⁷¹Yb³⁺ ions doped into a CaWO₄ crystal. We perform high-resolution spectroscopy of the excited state, and demonstrate all-optical coherent control of the electron-nuclear spin ensemble. We find narrow inhomogeneous broadening of the optical transitions of 185 MHz and radiative-lifetime-limited coherence time up to 0.75 ms. Next to this, we measure a spin-transition ensemble line width of 5 kHz and electron-nuclear spin coherence time reaching 0.15 seconds at zero magnetic field between 50 mK and 1 K temperatures. These results demonstrate the potential of ¹⁷¹Yb³⁺:CaWO₄ as a low-noise platform for building quantum technologies with ensemble-based memories, microwave-to-optical transducers, and optically addressable single-ion spin qubits.</p>