A coupled neutral-ionic photochemical model has been used to interpret the ionic composition of the Venusian dayside ionosphere measured by the orbiter retarding potential analyser (ORPA) experiment on board the NASA Pioneer-Venus orbiter spacecraft. The electron and ion temperatures also measured by the ORPA are used for calculating the plasma-diffusion coefficients and scale heights for ions. The neutral temperature profiles and the densities of neutral constituents, particularly CO2 and O, play key roles in the determination of the height profiles of the ionic constituents. All these quantities vary substantially in the Venusian thermosphere near the terminator; the models presented are representatives of the solar zenith angle ∼65°. The predicted O2+ densities below ∼200 km agree particularly well with observations by the ORPA, but the model values are significantly less than those measured by the orbiter ion mass spectrometer (OIMS). Models predict much smaller densities than observed values for all molecular ions above ∼200 km. The reason for the turn-up trend of the concentration gradient of molecular ions observed at these heights by both ORPA and OIMS is unknown. One of the models can predict O+ ion densities above ∼200 km compatible with observations, if an effective vertical escape flux (≲108 cm-2 sec-1) is assumed at the ionopause. The neutral air density required to explain the observed ion composition is about 1.4 times larger than the values measured by the orbiter neutral mass spectrometer (ONMS).