Intensity‐modulated photocurrent and photovoltage spectroscopy (IMPS/IMVS) are powerful tools in optoelectronics such as photoelectrochemistry and photovoltaics, as they demonstrate distinct charge dynamic processes at different frequencies. Unlike the material characterization techniques, IMPS/IMVS offer an approach for investigating the dynamic behavior of charge carriers and ions from the device perspective. This review examines IMPS/IMVS from both theories and experiments to understand the intricate charge dynamics in solar cells with various materials and structures. To accommodate different types of cells, four primary theoretical models including the rate constant model, drift‐diffusion model, equivalent circuit model, and distribution of relaxation times, are evaluated in detail. In the future, the incorporation of IMPS/IMVS with other time‐domain and frequency‐domain methods, along with imaging techniques, can significantly facilitate the characterization of charge dynamics with enhanced convenience, spatial dimensions, and accuracy.