In order to achieve a significant size reduction to get ultrasmall upconverting nanoparticles (UCNPs) following a thermal coprecipitation pathway, we identified two critical points: the UCNP precursor mixing and high-temperature heating steps. Significant differences could be observed according to the way the inorganic sodium and fluoride sources were mixed to the rare-earth oleate before the high-temperature heating step. More interestingly, accurate monitoring of the high-temperature heating step using microwave (MW) dielectric heating yielded major improvement toward ultrasmall UCNPs. Thus, hexagonal, Tm-doped sub-5-nm UCNPs with an unusual Na(Yb-Gd)F4 matrix with 53% Yb were produced, displaying satisfactory luminescence. Noticeably, MW heating was achieved in a weakly MW-absorbing oleic acid (OA)/octadecene mixture, and the influence of the OA content composition on the MW heating efficiency is discussed in this report.