We demonstrate laser induced DC electric fields in an all-glass vapor cell without bulk or thin film electrodes. The spatial field distribution is mapped by Rydberg electromagnetically induced transparency (EIT) spectroscopy. The fields are generated by a photoelectric effect and allow DC electric field tuning of up to 0.8 V/cm within the Rydberg EIT probe region. We explain the measured with a boundary-value electrostatic model. This work may inspire new approaches for DC electric field control in designing miniaturized atomic vapor cell devices. Limitations and other charge effects are also discussed.