Silver nanoparticles (AgNPs) were synthesized in skim natural rubber latex, the by-product from concentrated latex production. The role of ammonia was investigated by varying the concentration to be 0.217, 0.362, 0.377, 0.392, and 0.406 wt%. The emergence of AgNPs was detected by UV-visible spectrophotometer and electrical conductivity meter. Upon increasing ammonia concentration, the ABS peak increased to a maximum and slightly shifted to a higher wavelength and then it decreased afterward and slightly shifted to a lower wavelength. The shift of the ABS peak was consistent with the conductivity result. The kinetic model was proposed to explain the competition between the reducing effect and size-controlling effect of ammonia. The reducing effect seemed to dominate in the low range of concentration while the size-controlling effect via the formation of AgNH32+ complex ion was important in the higher range. The TEM figures evidently confirmed the effects.