The photografting of methacrylic acid (MAA) onto high-density polyethylene (HDPE) initiated by aliphatic ketones, butanone, pentanone, heptanone, etc. has been reported. When these ketones were used alone or just with ethanol, grafting did not occur. However, grafting took place when a proper butanone/water/ethanol mixed solvent was used. When the volume ratio of butanone was fixed, the grafting of MAA onto HDPE became easier with an increase in the volume ratio of water. The grafting of MAA onto HDPE became easier and faster with a decrease in the volume ratio of butanone. The grafting rate increased with the increase of monomer concentration. The nature of the alcohol also affected the self-initiation by aliphatic ketone; ethanol was found to be better than methanol. Possibly, hydrogen bond formed between aliphatic ketone and water increases the energy and lifetime of the excited state of the ketone, permitting it to act as a grafting and polymerisation initiator. FTIR characterization of the grafted samples proves the successful grafting of MAA onto HDPE. The water absorbency of the grafted samples increased almost linearly with the extent of grafting both in air and in water. The PE films grafted in the butanone/water/ethanol solvent adsorbed approximately 3040 mass% water per p-MAA.