Silica-based ceramics have been proposed for coating purposes to enhance dental and orthopedic titanium (Ti) implant bioactivity. The aim of this study was to investigate the influence of sphene-based bioceramic (CaO.TiO2.SiO2) coatings on implant osseointegration in vivo. Sphene coatings were obtained from preceramic polymers and nano-sized active precursors and deposited by an automatic airbrush. Twenty customized Ti implants, ten sphene-coated and ten uncoated rough implants were implanted into the proximal femurs of ten Sprague-Dawley rats. Overall, cortical and cancellous bone-to-implant contact (BIC) were determined using micro-computed tomography (micro-CT) at 14 and 28 days. Moreover, peri-implant bone healing was histologically and histomorphometrically evaluated. The white blood cell count in the synovial fluid of the knee joints, if present, was also assessed. No difference in the BIC values was observed between the sphene-coated and uncoated implants, overall and in the two bone compartments (p > 0.05). Delamination of the coating occurred in three cases. Consistently with micro-CT data, the histological evaluation revealed no differences between the two groups. In addition, no synovial fluid could be collected on the test side, thus confirming sphene biocompatibility. In conclusion, sphene coating was found to be a suitable material for biomedical applications. Further studies are needed to improve coating adhesion to the implants.