The crystallization behavior of the low band gap polymer poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3'''-di(2-octyldodecyl)2,2';5',2'';5'',2'''-quaterthiophen-5,5'''-diyl)] (PffBT4T-2OD) induced in printed mesoporous titania films with different pore sizes is studied to optimize the crystal orientation for an application in hybrid solar cells. The correlation between the crystal structure of PffBT4T-2OD and the titania pore size is investigated with a combination of grazing incidence wide-angle X-ray scattering (GIWAXS) and grazing incidence small-angle X-ray scattering (GISAXS). For comparison, poly(3-hexylthiophene) (P3HT) is also backfilled into the same four types of printed titania mesoporous scaffolds. Both, lattice constants and crystal sizes of edge-on oriented P3HT crystals decrease with increasing the titania pore size. Similarly and irrespective of the crystal orientation, a denser stacking of PffBT4T-2OD chains is found for larger pore sizes of the titania matrix. For an edge-on orientation, also bigger PffBT4T-2OD crystals are favorably formed in smaller pores, whereas for a face-on orientation, PffBT4T-2OD crystals increase with increasing size of the titania pores. Thus, the best ratio of face-on to edge-on crystals for PffBT4T-2OD is obtained through infiltration into large titania pores.