We employ first principles calculations to understand the surface termination dependent structural and magnetic properties of (0001) SmCo5 surface slabs. For our study, three different sub‐layer terminated surface slabs, namely Co3–(SmCo2–Co3)n, SmCo2–(Co3–SmCo2)n, and (Co3–SmCo2)n with thicknesses varying from n = 1 to n = 10, are considered. Our results revealed that the Co3 sub‐layer terminated surface slab (first case) has higher structural stability, spin polarization, and work function when compared to the other two cases and such terminated surface slabs can be potentially used for fabricating exchange‐coupled magnets.