The invention discloses a photovoltaic cell module packaging adhesive film, and a preparation method and application thereof. The photovoltaic cell module packaging adhesive film comprises a polyolefin adhesive film layer, and the polyolefin adhesive film layer comprises polyolefin resin, a cross-linking agent, an assistant cross-linking agent, a UV stabilizer, a UV absorbent, a heat stabilizer and a compatilizer. According to the invention, after the compatibilizer is added into a POE layer, the compatibilizer has polarity, so that the compatibilizer can be well compatible with the auxiliary agent, the auxiliary agent is not easy to separate out and is not easy to slip when being combined with a battery piece, the defects of the POE in the application of the solar battery are relieved, and meanwhile, the compatibilizer still has the advantages of the POE in the application of the solar battery. In addition, due to the addition of the compatilizer, the POE layer and the organic silicon layer can be effectively combined, and the invention further discloses a photovoltaic cell module composite packaging adhesive film comprising a polyolefin adhesive film layer and a silicon rubber film layer located on the surface of the polyolefin adhesive film layer.