A series of PPV films with different fluorescent emission colors are prepared using a facile approach. Modified from the conventional Wessling route, the labile sulfonium groups in the polymer precursor (pre-PPV) are partly substituted to various degrees by relatively stable methoxy groups, followed by a regular thermal elimination step to obtain PPV. Different chemical structures among these films are confirmed by IR and photophysical studies. Two film-preparative processes are compared and the films are studied by SEM and confocal fluorescent microscopy. From the same polymer precursor, different preparative processes result in PPV films with different morphologies but the same photophysical properties.