Films are prepared in the evaporation regime using a meniscus-guided coating method reported in our previous works . We analyze the degree of alignment, crystallinity of solution-coated films using a combination of cross polarized optical microscopy (CPOM), atomic force microscopy (AFM), UV-vis absorption spectroscopy, and GIXD. Figure summarizes CPOM images with coating directions parallel and 45º relative to the cross-polarized light. For highly aligned film with conjugated backbone oriented either parallel or perpendicular to the coating direction, the images would be darkest (brightest) when coating direction is oriented 0º (45º) relative to either axis of the cross-polarizers, and a higher degree of alignment and/or crystallinity results in larger intensity difference. Comparing the three solvents, films coated from amorphous network aggregates in CN solution show the largest intensity difference and highest birefringence, indicating a highly aligned nature of polymers in the film. Films coated from semicrystalline nanofibers in DCB show moderate degree of alignment due to twisting of the polymer nanofibers and the resulting twinned morphology . In contrast, films coated from semicrystalline agglomerates in decane barely show any alignment and birefringence even with a higher exposure time (171 ms) compared with those used for the other two films (52 ms). The CPOM characterizations at the macroscale are further substantiated by AFM measurements to reveal fibril orientation at mesoscale. Figure shows AFM phase images and corresponding orientation mapping analysis along with the pole figures of the fibril orientation distribution.