To explore the spatiotemporal evolution characteristics of pre-earthquake GPS TEC anomalies and their correlation with seismic activities, a statistical analysis was performed on pre-earthquake ionospheric GPS TEC anomalies associated with Ms ≥ 6.0 earthquakes in Mainland China from 2012 to 2022 using GPS TEC observational data. Two statistical metrics were adopted, namely average anomaly frequency and anomaly earthquake percentage. Classified statistical analyses were carried out from the perspectives of anomaly polarity, earthquake magnitude, focal depth, and different azimuths of the epicenter to systematically investigate the evolutionary characteristics of TEC anomalies from 30 days pre-earthquake to the earthquake day. The results show that the two core statistical indicators of pre-earthquake TEC anomalies present a significant increasing trend around the 25th, 15th, and 5th days before the earthquake and on the earthquake day. Moreover, the values of the two metrics corresponding to positive pre-earthquake TEC anomalies were higher than those corresponding to negative anomalies. Specifically, the values of the two metrics for pre-earthquake TEC anomalies of strong earthquakes with 6.8–7.6 were higher than those for 6.0–6.8 earthquakes. The spatial distribution of pre-earthquake TEC anomalies is characterized by inhomogeneity and time-dependent characteristics. Compared with earthquakes at a focal depth of 0–10 km, earthquakes at a focal depth of 10–20 km show more significant pre-earthquake TEC anomaly signals. Perturbation characteristics of pre-earthquake ionospheric GPS TEC were statistically analyzed, providing a reference for further elucidating the seismo-ionospheric coupling mechanism and identifying ionospheric precursors of earthquakes.