The quantum Cramér–Rao bound sets a fundamental limit on the accuracy of unbiased parameter estimation in quantum systems, relating the uncertainty in determining a parameter to the inverse of the quantum Fisher information. We experimentally demonstrate near saturation of the quantum Cramér–Rao bound in the phase estimation of a solid-state spin system, provided by a nitrogen-vacancy center in diamond. This is achieved by comparing the experimental uncertainty in phase estimation with an independent measurement of the related quantum Fisher information. The latter is independently extracted from coherent dynamical responses of the system under weak parametric modulations, without performing any quantum-state tomography. While optimal parameter estimation has already been observed for quantum devices involving a limited number of degrees of freedom, our method offers a versatile and powerful experimental tool to explore the Cramér–Rao bound and the quantum Fisher information in systems of higher complexity, as relevant for quantum technologies.