Porous silicon (PS) was incubated in an organic solution of metal acetylacetonates of Mn(acac)(3), Fe(acac)(3), Co(acac)(3), and Ni(acac)(2) (acac = MeCOCHCOMe) at room temperature. Crystal-like domains were found to be spontaneously self-assembled on PS surfaces by atomic force microscopy (AFM). Spectroscopic studies with attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS) revealed that the domains were grown from metal acetylacetonates. Current sensing atomic force microscopy (CSAFM) was used to measure the I-V curves of domains in nanoscale and specific step-jump currents on the manganese and cobalt acetylacetonate domains were surprisingly detected.