Highly ordered mixed framework mesoporous cubic (Im3m) or 2D hexagonal (p6m) thin films of (M1-x(Si - R)(x))O2-x/2 bearing organic groups (M = Ti or Zr, R = propylamine, mercaptopropyl or phenyl, x <= 0.2) are obtained by one-pot dip-coating. A second organic function (R' = hexadecyl, phenyl, sulfonate.) can be added by post-grafting with a molecule presenting a chelating group capable of anchoring to the M sites (phosphate, phosphonate, polyhydroxyphenol, carboxylate.) and a second organic group. This two-step procedure leads to bifunctional accessible mesopores. The role of post-synthesis stabilisation treatments, the alternative processes for template extraction, and the pore accessibility towards a second function are presented and discussed.