We present optical vector network analysis (OVNA) of an isotopically purified $^{166}$Er$^{3+}$:$^7$LiYF$_4$ crystal. The OVNA method is based on generation and detection of modulated optical sideband by using a radio-frequency vector network analyzer. This technique is widely used in the field of microwave photonics for the characterization of optical responses of optical devices such as filters and high-Q resonators. However, dense solid-state atomic ensembles induce a large phase shift on one of the optical sidebands which results in the appearance of extra features on the measured transmission response. We present a simple theoretical model which accurately describes the observed spectra and helps to reconstruct the absorption profile of a solid-state atomic ensemble as well as corresponding change of the refractive index in the vicinity of atomic resonances.
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