Monitoring spatiotemporal variations of ionospheric vertical total electron content (VTEC) is crucial for space weather and satellite positioning. In the present study, an enhanced neural network (ENN) model is proposed to capture the changing characteristics of ionospheric VTEC and compared with the traditional mathematical models, i.e. the POLYnomial (POLY) model, generalized trigonometric series function and spherical harmonic function (SHF) model. The ionospheric VTEC data obtained from 31 permanent global positioning system stations in the southwest region of China on 26 August and 8 September, 2017, were used to test the performance of the mentioned models under different Solar-geomagnetic conditions. The ENN model is derived from the ensemble learning method, and the disadvantage that simple backpropagation neural network learners that are not robust enough is weakened by the ENN model. After statistical analysis and single-frequency precise point positioning (SF-PPP) experiments, it is demonstrated that the ENN model is superior to the above three mathematical models, regardless of the solar-geomagnetic conditions. In terms of mean absolute error, root mean square error, standard deviation, and mean absolute percentage error, the ENN model outperforms the SHF model, which is the best mathematical model in the analysis, by 40.7%, 30.20%, 29.88%, 38.04% under quiet solar-geomagnetic conditions, and by 37.66%, 29.93%, 30.96%, 32.01% under active solar-geomagnetic conditions. In addition, the accuracy of the SF-PPP is greatly affected by the error caused by ionosphere. In the static SF-PPP experiment of this study, the ENN model can better correct ionospheric error. Under quiet and active solar-geomagnetic conditions, the SF-PPP accuracy can be improved by 85.1% and 85.2% with the ionosphere delay correction from the ENN model.