We present a search strategy for both Dirac and Majorana sterile neutrinos from the purely leptonic decays of W± → e± e± μ∓ν and μ± μ± e∓ν at the 14 TeV LHC. The discovery and exclusion limits for sterile neutrinos are shown using both the Cut-and-Count (CC) and Multi-Variate Analysis (MVA) methods. We also discriminate between Dirac and Majorana sterile neutrinos by exploiting a set of kinematic observables which differ between the Dirac and Majorana cases. We find that the MVA method, compared to the more common CC method, can greatly enhance the discovery and discrimination limits. Two benchmark points with sterile neutrino mass mN = 20 GeV and 50 GeV are tested. For an integrated luminosity of 3000 fb−1, sterile neutrinos can be found with 5σ significance if heavy-to-light neutrino mixings |UNe|2 ∼ |UNμ|2∼ 10−6, while Majorana vs. Dirac discrimination can be reached if at least one of the mixings is of order 10−5.