Electrochemical water splitting represents an ideal strategy for producing clean hydrogen as an energy carrier that serves as an alternative to fossil fuels. As an effective method for hydrogen production, an efficient inexpensive multifunctional electrocatalyst with high durability is designed. Herein, we describe the heterostructural design of a three-dimensional catalytic network with self-embedded CoNi2S4 nanograins grown on electrospun carbon nanofibers (CoNi2S4-CNFs) with anchored thin-layer reduced graphene oxide. This is achieved via facile electrospinning followed by carbonization, low-temperature sulfidation, and surface functionalization. As a bifunctional catalyst, CoNi2S4-CNFs exhibited robust high activity toward the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in an alkaline medium. The anchored ultrathin graphene oxide layer promoted the stability and durability of the catalytic network with an efficient path for the transportation of electrons. The rGO-anchored CoNi2S4-CNFs yielded overpotential values of 228 mV and 205 mV for the HER and OER, respectively, that drives a current density of 20 mA cm-2 in an alkaline medium. Notably, the excellent electrochemical properties are attributed to the functional effect of the CoNi2S4 on the CNF network. The ultrathin feature of rGO improved the durability of the catalytic network. Moreover, using the rGO-anchored CoNi2S4-CNFs as a cathode and anode in a two-electrode water splitting system required a cell voltage of only 1.55 V to reach a current density of 10 mA cm-2. These CNFs exhibited outstanding durability for 48 h. The present work offers new insight for the design of a catalytic network with a non-noble metal catalyst that exhibits excellent electrocatalytic activity and durability on the metal sulfides in overall water splitting.