We present the results of research on fast relaxation dynamics in the electronic excitation of silver nanoparticles synthesized in the presence of carboxylated amine complexons (NTA, Na 2 EDTA, DTPA) without any reductant or polymeric stabilizer. Unusual transient absorption dynamics in these objects after femtosecond laser irradiation was found, manifesting as the appearance of an additional long-lived bleaching band. The effect may be assigned to the inhomogeneous and porous shell of silver nanoparticles synthesized by such a procedure, as the consequence of a partial fragmentation of this shell due to heating under femtosecond laser excitation of plasmonic nanoparticles and subsequent electron–phonon energy relaxation.