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We prepare and analyze Rydberg states with orbital quantum numbers $\ell \le6$ using three-optical-photon electromagnetically-induced transparency (EIT)and radio-frequency (RF) dressing, and employ the high-$\ell$ states inelectric-field sensing. Rubidium-85 atoms in a room-temperature vapor cell arefirst promoted into the $25F_{5/2}$ state via Rydberg-EIT with three infraredlaser beams. Two RF dressing fields then (near-)resonantly couple $25 \ell$Rydberg states with high $\ell$. The dependence of the RF-dressed Rydberg-statelevel structure on RF powers, RF and laser frequencies is characterized usingEIT. Furthermore, we discuss the principles of DC-electric-field sensing usinghigh-$\ell$ Rydberg states, and experimentally demonstrate the method usingtest electric fields of $\lesssim$~50~V/m induced via photo-illumination of thevapor-cell wall. We measure the highly nonlinear dependence of theDC-electric-field strength on the power of the photo-illumination laser.Numerical calculations, which reproduce our experimental observations well,elucidate the underlying physics. Our study is relevant to high-precisionspectroscopy of high-$\ell$ Rydberg states, Rydberg-atom-based electric-fieldsensing, and plasma electric-field diagnostics.

High-angular-momentum Rydberg states in a room-temperature vapor cell for DC electric-field sensing