Gate structures and gate spacers, along with methods of forming such, are described. In an embodiment, a structure includes an active area on a substrate, a gate structure on the active area and over the substrate, and a low-k gate spacer on the active area and along a sidewall of the gate structure. The gate structure includes a conformal gate dielectric on the active area and includes a gate electrode over the conformal gate dielectric. The conformal gate dielectric extends vertically along a first sidewall of the low-k gate spacer. In some embodiments, the low-k gate spacer can be formed using a selective deposition process after a dummy gate structure has been removed in a replacement gate process.