Silver nanoparticles (NPs) of 5-15 nm are synthesized with the reduction of silver nitrate (AgNO₃) by formaldehyde (HCHO) and using polyethylenemine (PEI) as a stabilizer. Transmission electron microscopy (TEM) analysis shows the size of the Ag NPs increases with the increase of HCHO contents. The absorption and emission peaks of the original colloids are red shifted with increasing the size of Ag NPs. The absorption and emission peaks are at 344 nm, 349 nm, 357 nm, 362 nm, 364 nm and 444 nm, 458 nm, 519 nm, 534 nm, 550 nm, respectively. The fluorescence intensities of the silver colloids increase with increasing the NPs size (or the contents of HCHO). With the diluted fold increasing, the fluorescence intensity of the diluted silver colloids increases firstly then decreases. Compared with that of the original silver colloids, the emission peaks are blue shifted. For the diluted silver colloids, when the fluorescence intensity is maximum, the emission peaks are all near 444 nm. The 16-fold diluted silver colloid gets to the maximum emission intensity when the mole ratio of AgNO₃ and HCHO is 1:6.