Electro-optical control of on-chip photonic devices is an essential tool for efficient integrated photonics. Lithium niobate on insulator (LNOI) is an emerging platform for on-chip photonics due to its large electro-optic coefficient and high nonlinearity. Integrating quantum emitters into LNOI would extend their versatility in classic photonics to quantum computing and communication. Here, we incorporate rare-earth ion (REI) quantum emitters into electro-optical tunable lithium niobite (LN) thin films and demonstrate control of LN microcavities coupled to REIs over a frequency range of 160 GHz with 5 µs switching speed. Dynamic control of the cavities enables modulation of the Purcell enhancement of REIs with short time constants. Using Purcell enhancement, we show evidence of detecting single Yb3+ ions in LN cavities. Coupling quantum emitters in fast tunable photonic devices is an efficient method to shape the waveform of the emitter. It also offers a platform to encode quantum information in the integration of a spectral–temporal–spatial domain to achieve high levels of channel multiplexing, as well as an approach to generate deterministic single-photon sources.