A simple and highly efficient system for holographic recording based on a polyvinyl alcohol matrix is presented. A linear polyol is added to the solution made with the polymer and a xanthene dye in order to increase the photoinduced crosslinking rate. The optimization of the film fabrication process is determined experimentally. It is found that the length of the assistant unit, the position and the number of the attached hydroxyl groups is related with the saturation level and the shelf lifetime of the holographic planar grating. Also, host matrix and photoinitiator attributes are significant in the photosensitive medium response.