Pyrrole adsorption on Si(111)-(7x7) has been investigated using high-resolution electron energy loss spectroscopy (HREELS), thermal desorption spectroscopy, scanning tunneling microscopy (STM), and theoretical calculations. Compared to physisorbed pyrrole, chemisorption leads to the appearance of N-Si and Si-H vibrational features, together with the absence of N-H stretching mode. This clearly demonstrates the dissociative nature of pyrrole chemically binding on Si(111)-(7x7) through the breakage of N-H bond. Based on STM results, the resulting fragments of pyrrolyl and H atom are proposed to bind with an adatom and an adjacent rest atom, respectively. The STM images further reveal that the adsorption is site selective. The faulted center adatoms are most favored, followed by unfaulted center adatoms, faulted corner adatoms, and unfaulted corner adatoms. In addition, the chainlike pattern of reacted adatoms was observed, implying the possible existence of attractive interaction between adsorbed pyrrolyl and the precursor state. Theoretical calculation confirms that the dissociative adsorption with pyrrolyl bonded to an adatom and H atom to an adjacent rest atom is energetically favored compared to the associative cycloaddition involving the two alpha-carbon atoms of pyrrole and an adatom-rest atom pair. (C) 2003 American Institute of Physics.