Films consisting of surface-anchored metal-organic frameworks (SURMOFs) which are prepared by layer-by-layer deposition techniques can be used as highly oriented crystalline template structures for oligomerization processes. Herein, SURMOF films of Zn(bdc) (1) and, Cu(bpdc) (2) were prepared, which consist of lamellar ordered 2D MOF sheets forming 1D channels as the host structures for oligomerization of terthiophene (Tth) and, 3,4-ethylenedioxythiophene (EDOT), respectively. After SURMOF preparation, the pores were filled either with Tth or EDOT and the oligomerization was initiated by oxidizing agents, such as I2 and FeCl3. Using matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-ToF/MS), the short chains of polyterthiophene (PTth) and poly(3,4-ethylenedioxythiophene) (PEDOT) were characterized. FT-IR and Raman spectroscopy further confirmed the presence of oligomers inside the pores of the SURMOFs. Using the SURMOF thin films as template, a homogeneously distributed conductive MOF-PEDOT composite coating can be achieved, with potential applications in optoelectronics.