Augmentation of the Global Navigation Satellite System by low earth orbit (LEO) satellites is a promising approach benefiting from the advantages of LEO satellites. This, however, requires errors and biases in the satellite downlink navigation signals to be calibrated, modeled, or eliminated. This contribution introduces an approach for in-orbit calibration of the phase center offsets (PCOs) and code hardware delays of the LEO downlink navigation signal transmitter/antenna. Using the satellite geometries of Sentinel-3B and Sentinel-6A as examples, the study analyzed the formal precision and bias influences for potential downlink antenna PCOs and hardware delays of LEO satellites under different ground network distributions, and processing periods. It was found that increasing the number of tracking stations and processing periods can improve the formal precision of PCOs and hardware delay. Less than 3.5 mm and 3 cm, respectively, can be achieved with 10 stations and 6 processing days. The bias projections of the real-time LEO satellite orbital and clock errors can reach below 3 mm in such a case. For near-polar LEO satellites, stations in polar areas are essential for strengthening the observation model.