A jointed experimental and theoretical investigation pointing out new insights about the microscopic mechanism of the VOCs (volatile organic compounds) photocatalytic elimination by TiO2 has been done. Methane, hexane, isooctane, acetone and methanol have been photomineralized in a batch reactor. Values of K (adsorption constant on TiO2) and k (mineralization rate constant) of the five VOCs (treating the kinetic data through a Langmuir- Hinshelwood approach) have been determined. Recorded K and k values and performed theoretical calculations allowed us to suggest the involvement of an electron transfer step between the VOC and the hole, TiO2(h+), as the rate determining one.