Significant advances have been made recently in the area of organic electronics and optoelectronics based on small molecules as a result of an improved chemistry and a better technology. Together with light emitting diodes and solar cells, transistors are among the most studied components. The development of new semiconductors induced a real improvement in organic thin film transistor's performances. Additionally, the synthesis of new soluble and air-stable molecules with the ability to process the active materials at low temperatures over large areas on substrates such as plastic or paper provide unique technologies and generate new applications. However the control of the solid state structure has emerged as essential to realize the full intrinsic potential that organic semiconductors possess. Atomic force microscopy (AFM) was likely to contribute to a further advancement of knowledge. The ability of the AFM to produce three dimensional maps at the micro-and nanometer scale has greatly increased its popularity as an imaging tool. Recently, distyryl-oligothiophenes and their derivatives appear as a new class of molecular semiconductors. Detailed morphological studies of organic active layers based on such new semiconductors involved in organic thin film transistors (OTFTs) have brought a large knowledge about the impact of chemical and physico-chemical aspects on charge transport efficiency.