Magnetocaloric and magnetoresistance properties originated from a metamagnetic structural transition were investigated in a Fe-doped Ni46.8Mn38.1Sn11.6Fe3.5 alloy. After annealing, the alloy exhibited the intermartensite phase that contributed to the multiple abrupt magnetization and resistivity changes during heating process of martensite transformation. As a result, three successive magnetic entropy change ΔSM peaks of 10.7, 14.5 and 9.7 J/kg·K at temperatures 275, 279 and 285 K respectively were observed, which was responsible for a wide working temperature span ΔTFWHM of 273–287 K and thus a large effective refrigeration capacity RCeff of 98.1 J/kg under 5.0 T. At the same time, a large negative magnetoresistance MR (e.g. over 26.7% at 275 K) was also revealed during heating process under 5.0 T. Such multi-functional magnetocaloric and magnetoresistance effects render Ni–Mn–Sn–Fe alloys promising working materials for magnetic refrigerants, information storage and thermal magnetoelectricity conversions.