Ca-Co-Mn-Zn-doped Sr-hexaferrites with a cation composition of Sr0.7Ca0.3Fen-0.6Co0.2Mn0.2Zn0.2 were prepared using conventional solid-state reaction processes by varying Fe contents (10 ≤ n ≤ 17). The hexaferrite sample with an Fe content of 10 ≤ n ≤ 13 exhibited composite phases of M-type and W-type hexaferrite on calcining at 1250°C in air while the samples calcined at 1200°C in air exhibited only the M-type phase. The sample with n = 13 exhibited a saturation magnetization (MS) of 70.7, 75.3, 78.0emu/g after performing calcination at 1200, 1250, and 1300°C, respectively. MS higher than that of the non-doped M-type Sr-hexaferrite (~ 72emu/g) sample is attributed to the volume portion of the high-MS W-type phase. It is also revealed that the co-doping of Ca, Co, and Zn is crucial for the formation of the W-type phase in the sample calcined at 1250°C in air.