We report results from the first search for $\nu_\mu\to\nu_e$ transitions by the NOvA experiment. In an exposure equivalent to $2.74\times10^{20}$ protons-on-target in the upgraded NuMI beam at Fermilab, we observe 6 events in the Far Detector, compared to a background expectation of $0.99\pm0.11$ (syst.) events based on the Near Detector measurement. A secondary analysis observes 11 events with a background of $1.07\pm0.14$ (syst.). The $3.3\sigma$ excess of events observed in the primary analysis disfavors $0.1\pi