Pure　TiO2　and　Eu-doped　TiO2　hollow　microspheres　were　prepared　by　Sol-Gel　method　and　characterized　by　techniques　such　as　XRD,　SEM,　TEM,　HRTEM,　BET　and　XPS.　Photocatalytic　degradation　of　methylene　blue　(MB)　in　aqueous　solution　was　used　as　a　probe　reaction　to　evaluate　their　photocatalytic　activity.　The　experimental　results　show　that　the　dosage　of　TBOT　has　a　great　effect　on　the　morphology　of　TiO2　hollow　microspheres.　When　the　dosage　of　TBOT　is　1.5　mL,　the　obtained　hollow　microspheres　disperse　well　and　show　clear　structure.　XRD　pattern　indicates　that　TiO2　hollow　microspheres　calcined　at　400　degrees　C　present　anatase　structure　and　Eu-doped　ones　can　restrain　the　anatase　phase　from　converting　to　rutile　phase.　The　experimental　results　suggest　that　Eu-doped　can　obviously　improve　the　photocatalytic　activity　of　TiO2　hollow　microsphere　and　when　the　doping　of　Eu　is　0.7%,　the　photocatalytic　degradation　reaches　the　best　because　of　its　highest　surface　area　and　smallest　crystallize　size　and　pore　diameter.