In this study, wettability was employed to evaluate the effect of alkali activation by NaOH on different fly ash (FA) particle sizes. The results indicated that the surface wettability of FA particles with 13.8 μm increased from 0.025 g2/s to 0.034 g2/s after activation by the NaOH solution, which is suitable for silane modification and electroless plating. X-ray photoelectron spectroscopy (XPS) was used to analyze whether three kinds of silane coupling agents coated on FA surfaces could detect the chemical bonds between silane coupling agents coated on the FA surface and silver layers by shortening the plating time. The XPS results demonstrated that N-Ag coordination bonds can be detected by reducing silver plating time to 2 min for Ag-plated FA modified by N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (KH792). However, there were no chemical bonds detected for Ag-plated FA modified by γ-(2,3-epoxypropoxy)propytrimethoxysilane (KH560) and methyltrimethoxysilane (MTMS), even when the satellite peak of Ag disappeared after plating for 80 s. The SEM showed that Ag particles agglomerated on FA surfaces, and even a bare surface was found after modification by KH560 and MTMS, which further proved no chemical bonds between silver layers and the silane coupling agents.