Based on the previously discussed hypothesis concerning the mechanism of conversion of paraffins, we have modified the structure of VPO catalysts by developing the (220) plane of VOHPO4·0.5H2O and introducing a bismuth additive. We have shown that this leads to an increase in the P/V ratio on the surface, an increase in the number of Lewis centers and the strength of such centers, and a change in the ratio of Lewis centers to Bronsted centers. The change in the surface characteristics of the samples, in accordance with the hypotheses, improves their properties in oxidative dehydrogenation of ethane, increasing the catalytic activity and the yield of the target product ethylene.