We report the first simultaneous observations of total electron content (TEC), radio signal scintillation, and precise point positioning (PPP) variation associated with Strong Thermal Emission Velocity Enhancement (STEVE) emissions during a 26 March 2008 storm-time substorm. Despite that the mid-latitude trough total electron content (TEC) decreases during the substorm overall, interestingly, we found an unexpected TEC enhancement (by ~2 TECU) during STEVE. Enhancement of vertical TEC and phase scintillation was highly localized to STEVE within a thin latitudinal band of 1°. As STEVE descended equatorward, TEC enhancement was found at and slightly poleward of the optical emission. PPP exhibited enhanced variation across a 3° latitudinal range around STEVE and indicated increased GNSS positioning error. We suggest that TEC enhancement during STEVE creates local TEC structures in the ionosphere that degrade Global Navigation Satellite Systems (GNSS) signals and PPP performance. The TEC enhancement may be created by particle precipitation, Pedersen drift across STEVE, neutral wind, or plasma instability.