A growing number of SmallSat/CubeSat constellations with high-rate (50–100 Hz) global navigation satellite system radio occultations (GNSS-RO) as well as low-rate (1 Hz) precise orbit determination (GNSS-POD) limb-viewing capabilities provide unprecedented spatial and temporal sampling rates for ionospheric studies. In the F-region electron density (Ne) retrieval process, instead of the conventional onion-peeling (OP) inversion, an optimal estimation (OE) inversion technique was recently developed using total electron content measurements acquired by GNSS-POD link. The new technique is applied to data acquired from the COSMIC-1, COSMIC-2, and Spire constellations. Although both OE and OP techniques use the Abel weighting function in Ne inversion, OE significantly differs in its performance, especially in the lower F- and E-regions. In this work, we evaluate and compare newly derived data sets using F2 peak properties with other space-based and ground-based observations. We determine the F2 peak Ne (NmF2) and its altitude (hmF2), and compare them with the OP-retrieved values. Good agreement is observed between the two techniques for both NmF2 and hmF2. In addition, we also utilize autoscaled F2 peak measurements from a number of worldwide Digisonde stations (∼30). The diurnal sensitivity and latitudinal variability of the F2 peak between the two techniques are carefully studied at these locations. Good agreement is observed between OE-retrieved NmF2 and Digisonde-measured NmF2. However, significant differences appear between OE-retrieved hmF2 and Digisonde-measured hmF2. During the daytime, Digisonde-measured hmF2 remains ∼25–45 km below the OE-retrieved hmF2, especially at mid and high latitudes. We also incorporate F-region Ne measurements from two incoherent scatter radar observations at high latitudes, located in the North American (Millstone Hill) and European (EISCAT at Tromso) sectors. The radar measurements show good agreement with OE-retrieved values. Although there are several possible sources of error in the ionogram-derived Ne profiles, our further analysis on F1 and F2 layers indicates that the low Digisonde hmF2 is caused by the autoscaled method, which tends to detect a height systematically below the F2 peak when the F1 layer is present.