A new method that allows for mold-free, rapid and easy-to-use prototyping of microfluidic devices comprising channels, access holes and surface modified patterns, is presented. The innovative method is based on direct photolithographic patterning of an off-stoichiometry thiol-ene (OSTE) polymer formulation, tailor-made for photolithography, which offers unprecedented spatial resolution and allows for efficient, robust and reliable, room temperature surface modification and glue-free, covalent room temperature bonding. This mold-free process does not require cleanroom equipment and therefore allows for rapid, i.e. less than one hour, design-fabricate-test cycles, using a material suited for larger scale production. The excellent photolithographic properties of this new OSTE formulation allow for unprecedented, for thiol-ene polymer systems, resolution patterning in hundreds of micrometers thick layers, 200 µm thick in this work. Moreover, we demonstrated robust (covalent) and spatially-controlled modification of the microchannel surfaces with a contact angle of 76 degrees to hydrophobic/hydrophilic areas with contact angles of 102 and 43 degrees, respectively.