We have investigated the plasmonic properties of heterostructures that consist of gold nanosphere (NSs) with average diameters of 60 nm, 40 nm and 20 nm on poly (ethylene glycol) (PEG) brushes by using ultrafast pump-probe spectroscopy experiments. Gold NSs start to behave like gold nanorods with increasing number of immobilization cycles due to the close proximity. Gold NSs immobilized by 3 and 5 deposition cycles show longitudinal modes of plasmon bands at long wavelengths which are characteristic behaviors for gold nanorods. Increasing the number of immobilization cycle also increase relaxation times of samples due to the close proximity. Linear absorption spectra and scanning electron microscopy images show that there are close packing assemblies for heterostructures containing 20 nm gold NSs as the small particle. Ultrafast electron transfer (<100 fs) occurs between transverse and longitudinal modes by exciting the samples at both 520 nm and 650 nm. Further, experimental results indicate that, heterostructures with the small particles have faster relaxation times than other heterostructures due to closed packing of 20 nm gold NSs. (C) 2017 Elsevier B.V. All rights reserved.