We have performed density functional cluster model calculations to explore the mechanism and regioselectivity for the reactions of propylene oxide with X(100)-2x1 surfaces (X = C, Si, and Ge). The computations reveal the following: (i) the reactions on Si(100) and Ge(100) are barrierless and highly exothermic; (ii) the reactions on X(100) (X = Si and Ge) are initiated by the formation of a dative-bonded precursor state followed by regioselective cleavage of the C2-O bond (C2 directly connected to the methyl-substituent) in propylene oxide, giving rise to a five-membered ring surface species; and (iii) the reaction on C(100), although highly exothermic, requires a large activation energy and would be kinetically forbidden at room temperature.