Hot ethanolic mixts. of hydrated Zn(II)- and Fe(II)-carboxylates (acetate and lactate) react to form yellow-orange colored Fe(III)xZnyOzOHw heteroclusters showing pronounced electronic resonances in the optical UV absorption spectra. On the addn. of LiOH to these polymol. sols, stable nanoparticulate Fe(III)-ZnO colloids are formed. During colloidal growth, 2-4 nm sized weakly crystd. Wurtzite nanoparticles are exclusively formed even in the presence of high Fe content up to 20 at.%. The presence of Fe(III) in the ZnO condensation process retards the nanoparticle growth and blocks the thermal crystn. and size enhancement up to 250 °C. The produced 0.5 M Fe(III)-ZnO sols are useful for film formation processes. From at. force microscopy-AFM, SEM-SEM and X-ray diffraction-XRD studies, we note important differences in shape and morphol. of the thermally annealed Fe(III)-ZnO layers depending on the iron carboxylate employed. Surprisingly, Fe(II)-lactate derived coatings are carrying vertically oriented cone-shaped aggregates composed of 60-120 nm long primary nanorods. Contrary, Fe(II)-acetate based synthesis gave sand-dune like film morphologies contg. spherical 12 nm sized nanocrystallites. All film samples possess mesoporosity with pore size ranging between 5 and 20 nm.