Doped zinc-phosphate (ZP) glasses of compositions ZP:Ag:Au and ZP:Ag:Rb were synthesized by the melt quenching method both without and with the use of additional heat post-treatment at T = 500 °C. In the obtained glasses, bimetallic nanoparticles (NPs) of compositions AgAu and AgRb were formed respectively, along with the silver NPs. The ratio of the Ag and Au components in the AgAu NPs was estimated. The use of post T-treatment in the synthesis of glasses of composition ZP:Ag:Au led to an increase in the average size of NPs from ~4.5 nm to ~12.1 nm. Besides, both the minimum size of the NPs and the fraction of larger NPs with sizes ?15 nm increased. T-treatment for the sample of composition ZP:Ag:Rb did not lead to a noticeable change in the average size of NPs, which remained within 4.5…4.7 nm. However, the fraction of larger NPs (up to 20 nm) increased in the size distribution. A 3.5-fold increase in the intensity of Nd3+ ions emission at the wavelength of 1060 nm, excited by radiation with ?excit = 525 nm in the sample ZP:Ag:Au:Nd, was obtained compared to the glass sample without plasmonic metals. The decisive role of subnanometer nanoclusters (NCs) and NPs of the compositions Ag and AgAu in the observed increase of Nd emission intensity upon excitation with a wavelength of ?excit = 525 nm was established. The use of the post T-treatment for the glass of composition ZP:Ag:Au:Nd led to the transformation of Ag NCs into NPs, which resulted in a decrease in the enhancement of the Nd3+ ions emission intensity compared to the sample without heat treatment. When Nd3+ ions were excited by radiation with ?excit = 785 nm, far from the excitation of LSPR in Ag and AgAu NPs, the T-treatment performed during the synthesis of glass with composition ZP:Ag:Au:Nd did not noticeably affect the intensity of the Nd3+ emission line, which indicated the absence of clustering of neodymium ions at the elevated temperatures and duration of post-treatment used.