The palladium catalysts prepared using carbon nanoglobules (CNGs) as the support and containing no more than 2 wt% Pd were shown to be highly effective for the liquid-phase hydrogenation of ethyl 4-nitrobenzoate under mild conditions. Regardless of the kind of CNGs and the catalyst preparation method, the most of the Pd/CNGs catalysts allow achieving a complete conversion of substrate giving benzocaine in a 100% yield. The Pd/CNGs catalyst is easily recycled many times without loss of its catalytic performance. The results obtained may be useful for the development of effective Pd/C catalysts for chemoselective hydrogenation of various nitroarenes. Display omitted •Pd/CNGs is a promising catalyst for hydrogenation of ethyl 4-nitrobenzoate.•Pd/CNGs allow obtaining benzocaine in a 100% yield.•CNGs kind affects the reducibility and dispersion state of supported Pd.•Pd/CNGs can be a practical catalyst for synthesis of benzocaine and other anilines.