In recent years, numerous low earth orbit (LEO) satellites have been launched for different scientific tasks such as the Earth’s magnetic field, gravity recovering and ocean altimetry. The LEO satellites can cover the ocean area and are less affected by atmospheric delays and multipath errors, which provides new opportunities for calibrating the phase biases of the Global Navigation Satellite System (GNSS). In this contribution, we propose an alternative approach for uncalibrated phase delay (UPD) estimation by making full use of onboard observations of LEO satellites. Stable wide-lane (WL) and narrow-lane (NL) UPDs can be obtained from spaceborne GNSS observations and agree well with the UPD products derived from 106 IGS stations. To further verify the feasibility of the proposed method for UPD estimation, zero-difference (ZD) ambiguity resolution (AR) for precise point positioning (PPP) and LEO precise orbit determination (POD) are implemented. After applying the LEO-based UPDs, the averaged convergence time for PPP AR can be reduced to 15.2 min, with an improvement of 24% compared to float solutions. As for LEO AR, the fixing rates of WL and NL ambiguities exceed 98 and 92%, respectively. The accuracies of ambiguity-fixed orbits are validated by comparing with external satellite laser ranging (SLR) and K-band ranging (KBR) observations. Compared to float solutions, the standard deviations (STDs) of SLR residuals can be reduced by 8 ~ 43%, and the KBR residuals of 3.75 mm can be achieved for fixed solutions using LEO-based UPDs, with an improvement of 60%. Although the current UPD results derived from LEO satellites are slightly worse than those of ground-based UPD, it is anticipated that the performance of LEO-based UPD can be further improved in the near future with the rapidly increasing number of LEO satellites and the continuous refinements of the POD method.