We report significantly improved silicon nanowire/TiO2 n+-n heterojunction solar cells prepared by sol-gel synthesis of TiO2 thin film atop vertically aligned silicon nanowire arrays obtained by facile metal-assisted wet electroless chemical etching of a bulk highly doped n-type silicon wafer. As we show here, chemical treatment of the nanowire arrays prior to depositing the sol-gel precursor has dramatic consequences on the device performance. While hydrofluoric treatment to remove the native oxide already improves significantly the device performances, hydrobromic (HBr) treatment consistently yields by far the best device performances with power conversion efficiencies ranging between 4.2 and 6.2% with fill factors up to 60% under AM 1.5G illumination. In addition to yield high-quality and easy to produce solar cell devices, these findings regarding the surface treatment of silicon nanowires with HBr suggest that HBr could contribute to the enhancement of the device performance not only for solar cells but also for other optoelectronics devices based on semiconductor nanostructures.