Abstract We report the studies of various conjugated polymer thin films with near-field scanning optical microscopy, NSOM. Firstly, it is shown that MEH-PPV thin film undergoes significant changes in film morphology upon thermal annealing. The once homogeneous morphology becomes inhomogeneous after annealing. Secondly, polarization near-field measurements reveal mesoscale polymer ordering in PPV thin film. The average domain size and the coefficient for linear dichroism were studied as a function of film thickness. Finally, phase separation in polymer blend film was directly observed by transmission NSOM. Time-resolved fluorescence spectra indicate that the phase domains are decomposed of different fractions of the two constituent polymers. The near-field optical microscopy was also used to write lithographic patterns with a resolution of 100 nm, exceeding the diffraction limit.