Poly(allylamine　hydrochloride)　(PAAH),　a　mimic　of　biopolyamines,　was　used　to　induce　the　mineralization　of　titania　at　room-temperature,　hollow　spheres　with　a　mixed　phase　(anatase　and　rutile)　were　obtained,　and　the　fine　anatase　and　rutile　nanocrystals　were　observed　mixing　at　the　sub-10　nm　scale　on　the　hollow　spheres.　The　structural　information　about　the　precipitated　titania　gained　by　transmission　electron　microscopy,　X-ray　diffraction,　and　X-ray　photoelectron　spectroscopy　revealed　a　distinct　dependence　of　the　polymorph　and　morphology　of　the　titania　precipitates　on　the　molecular　structure　of　the　polyamines　and　titanium　precursors.　Moreover,　we　have　observed　the　phase　transformation　from　anatase　to　rutile　in　the　formation　process　of　hollow　spheres,　and　it　was　suggested　that　the　protonated　amino　groups　on　PAAH　played　key　roles　in　the　transformation　of　both　polymorphs　and　morphologies　of　titania.　Additionally,　poly(diallyldimethylammonium　chloride)　(PDDA),　a　long　chain　quaternary　ammonium　polymer,　was　used　as　another　catalytic　template　for　the　synthesis　of　titania,　which　also　led　to　a　hollow　structure　with　a　mixture　of　anatase　and　TiO2-B.