A study of photoinduced processes in pyridine-based gels is presented, Poly(4-vinyl pyridine) dissolved in pyridine with water addition forms a photosensitive material. Under irradiation at the main absorption at 250 nm, a new intense absorption at 360 nm and an emission at 515 nm appeared. Upon continuation of radiation, together with an increase in the intensity of the new absorption, a prolonged tail through the whole visible range is observed. A new far red-shifted emission arises in correlation with the absorption spectrum changes. The presence of lower energy aggregates leads to polymer morphology changes. Short-range aggregates enhance polymer-polymer interactions. Long range aggregates have a tendency to crystallize. The photoinduced morphology changes was studied by transmission electron microscopy (TEM) of the polymer thin film and differential scanning calorimetry (DSC) of the gel. Phase separated species, micelles-like forms with domain size over 200 nm, and nanocrystals with average size 20-30 nm are demonstrated.