Molybdenum diselenide (MoSe2) has been considered as a promising electrocatalyst for the hydrogen evolution reaction (HER), having great significance in the exploration of catalysts for green energy production. To obtain excellent electrocatalytic properties of MoSe2, the structural design of materials has become a commonly-used strategy. Hence, the combination of hexadecyl trimethyl ammonium bromide (CTAB) and polyethylene-polypropylene glycol (F68) was employed during hydrothermal process to modify the structure of MoSe2. Compared with using only one surfactant (CTAB or F68), MoSe2 catalyst represents better surface activity, more active sites and enhanced catalytic activity in the presence of dual surfactants. The as-prepared MoSe2[email protected] catalyst achieves an excellent HER activity with an overpotential of 189 mV versus the reversible hydrogen electrode (RHE) at a current density of 10 mA cm−2 and a low Tafel slope of 62 mV dec−1. Therefore, this work paves a way to prepare electrocatalysts with dual surfactants existence, which is greatly attractive for an optimizing electrocatalyst performance in a more efficient way.