Suprathermal electrons (~0.1–10 keV) in the inner magnetosphere are usually observed in a 90°‐peaked pitch angle distribution, formed due to the conservation of the first and second adiabatic invariants as they are transported from the plasma sheet. We report a peculiar field‐aligned suprathermal electron (FASE) distribution measured by Van Allen Probes, where parallel fluxes are 1 order of magnitude higher than perpendicular fluxes. Those FASEs are found to be closely correlated with large‐amplitude hiss waves and are observed around the Landau resonant energies. We demonstrate, using quasilinear diffusion simulations, that hiss waves can rapidly accelerate suprathermal electrons through Landau resonance and create the observed FASE population. The proposed mechanism potentially has broad implications for suprathermal electron dynamics as well as whistler mode waves in the Earth's magnetosphere and has been demonstrated in the Jovian magnetosphere. Plain Language Summary Hiss waves are structureless and incoherent “hissy” emissions found in the magnetized near‐Earth space, typically in a frequency range from 0.1 to 2 kHz. Hiss waves have traditionally been treated as an energetic electron removal mechanism, because they can precipitate energetic electrons through resonant interactions and cause electron loss into the atmosphere. Here we show, by presenting observations from NASA's Van Allen Probes, that intense hiss waves are accompanied by enhancements of field‐aligned suprathermal electrons. We propose that hiss waves can accelerate suprathermal electrons as they travel at the same speed in the direction along the magnetic field. Computer simulations successfully reproduce the rapid enhancement of field‐aligned suprathermal electrons under the impact of hiss waves, with detailed features similar to observations. Key Points Pronounced field‐aligned suprathermal electron enhancements are observed in correlation with intense hiss waves Numerical simulations reproduce field‐aligned electron distributions similar to observations Intense hiss waves can accelerate field‐aligned suprathermal electrons via Landau resonance on a timescale of several minutes