Alkenes are known to react with hydrogen-terminated silicon surfaces to produce robust organic monolayers that are attached to the surface via covalent Si-C bonds. In this report we investigate the dependence of the rate of alkylation of porous silicon samples on the reaction time using photochemical initiation. The kinetics of the photochemical alkylation of hydrogen-terminated porous silicon by undec-1-ene in toluene were observed to be pseudo first order, however the apparent rate constant decreased as the concentration of undec-1-ene increased. This behaviour is opposite to what would be expected if the rate-limiting process was an elementary chemical reaction step involving the alkene. Instead, it suggests that transport of the alkene to reactive sites and in the correct orientation is the rate-limiting step. Comparison of the rates of alkylation of porous silicon by undec-1-ene and dimethoxytrityl (DMT)-undecenol is consistent with such an interpretation as the bulky DMT headgroup gives a lower rate of alkylation. The diffusion of some simple redox-active probe molecules in porous silicon was investigated using a scanning electrochemical microscope (SECM). The probe molecules are converted at diffusion-controlled rate at an inlaid disk ultramicroelectrode (UME) consisting of the cross-section of a microwire sealed in glass. If the microelectrode is placed a short distance above the porous silicon, the microelectrode current depends on kinetics of the electrochemical reactions at the porous silicon and the mass transport properties within the open thin layer cell formed by the microelectrode and the alkylated porous silicon. In order to differentiate the effects of finite heterogeneous kinetics at silicon from diffusion limitations, current-distance curves were fitted over a wide range of applied potentials (on the Si) and it was observed that the diffusion coefficient in the porous layer was strongly anisotropic. The measured diffusion rates are comparable to those in bulk water along the pores, but with negligible diffusion between pores. This indicates that few pore-pore interconnections exist in the porous silicon.