A new activation method has been developed for initiating electroless metal deposition on silicon substrates without SnCl2 sensitization and roughening condition. Silicon wafers are first coated with thiol-terminated self-assembled monolayers (SAMs), and then catalyzed with a stable tin-free Pd(II)-based colloidal solution. Atomic force microscopy (AFM), Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) were used to characterize the step-by-step surfaces and study the binding mechanism of Pd(Ⅱ) with SAMs onto surfaces. Results show that Pd(II) oligomer particles are chemisorbed on pendant thiol surfaces through S-Pd bonds. This process involves fewer steps than the conventional Sn/Pd combined activation one. Furthermore, the chemical bound initiator possesses longevity and can be stored for a long time before metallization.