Calcium phosphate (CaP) coatings are of continuing significant interest due to their ability to directly promote bone cell differentiation. Whereas sputter deposited CaP coatings have much to offer in this regard, in the as-deposited state they are inherently amorphous and readily undergo rapid dissolution. This behaviour severely limits their ability to support bone cell adhesion and the subsequent events of proliferation and/or differentiation without subsequent processing such as thermal annealing. Removal of the need for this additional processing step would significantly increase their utility. This paper reports a study of the use of nano-porous titania substrates to directly control the rate of dissolution of thin amorphous as-deposited CaP sputter coatings. Titania nanotubes with different pore sizes were prepared by electrochemical anodization of titanium foils and sputter coated with CaP. Dissolution studies were performed on the as-deposited CaP layers in cell culture media for periods of up to 21 days. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) analysis confirmed the potential of the nanotubes to prolong the rate of loss of CaP over the entire 21 day period as compared to coatings prepared on flat polished titanium surfaces, which dissolved completely in less than 48 h. The CaP coated titania nanotube surfaces showed high levels of osteoblast attachment and proliferation with no signs of cell death. Alkaline phosphatase (ALP) activity measurements at 21 days indicated that the highest levels of osteoblast differentiation occurred on CaP thin films deposited onto titania nanotubes with an average pore size of 30 ± 7.5 nm and tube length of 1.3 ± 0.2 μm. These results indicate that prolonged availability of the as-deposited sputtered CaP can be provided for by use of a substrate surface comprising titania nanotubes. Moreover, nanotube pore size and tube length affect the rate of CaP dissolution and attendant cell behaviour thereon.