A polyolefin composite film having a five-layer structure consisting of a surface layer [i], an intermediate layer [iii], a core layer [ii], an intermediate layer [iii] and a surface layer [i] in this order, wherein the surface layer [i] is formed from a propylene resin composition that comprises: a propylene/1-butene random copolymer and/or a 1-butene/α-olefin copolymer in an amount of 0 to 50 wt%, and a propylene polymer in an amount of 50 to 100 wt%, provided that the total amount of, and in the surface layer is 100 wt%; wherein the core layer [ii] is formed from a propylene resin composition that comprises: a crystalline polypropylene in an amount of 70 to 100 wt%, and the propylene/1-butene random copolymer in an amount of 0 to 30 wt%, provided that the total amount of and in the core layer is 100 wt%; and wherein the intermediate layer [iii] is formed from a propylene resin composition that comprises: the crystalline polypropylene in an amount of 50 to 95 wt%, and the propylene/1-butene random copolymer in an amount of 50 to 5 wt%, provided that the total amount of and in the intermediate layer is 100 wt%, wherein the propylene/1-butene random copolymer comprises 60 to 80 mol% of a unit derived from propylene and 20 to 40 mol% of a unit derived from 1-butene and has a melting point of 140°C or lower or a melting point that is not observed, the propylene polymer comprises 85 to 97 mol% of a unit derived from propylene and 3 to 15 mol% of a unit derived from C2-10 α-olefins excluding propylene and has a melting point of 120 to 170°C, crystalline polypropylene comprises 98 to 100 mol% of a unit derived from propylene and 0 to 2 mol% of C2-10 α-olefins excluding propylene and has a melting point of 150 to 170°C, and the 1-butene/α-olefin copolymer comprises 50 to 95 mol% of a unit derived from 1-butene and 50 to 5 mol% of a unit derived from C2-10 α-olefins excluding 1-butene. a propylene/1-butene random copolymer and/or a 1-butene/α-olefin copolymer in an amount of 0 to 50 wt%, and a propylene polymer in an amount of 50 to 100 wt%, provided that the total amount of, and in the surface layer is 100 wt%; wherein the core layer [ii] is formed from a propylene resin composition that comprises: a crystalline polypropylene in an amount of 70 to 100 wt%, and the propylene/1-butene random copolymer in an amount of 0 to 30 wt%, provided that the total amount of and in the core layer is 100 wt%; and a crystalline polypropylene in an amount of 70 to 100 wt%, and the propylene/1-butene random copolymer in an amount of 0 to 30 wt%, provided that the total amount of and in the core layer is 100 wt%; and wherein the intermediate layer [iii] is formed from a propylene resin composition that comprises: the crystalline polypropylene in an amount of 50 to 95 wt%, and the propylene/1-butene random copolymer in an amount of 50 to 5 wt%, provided that the total amount of and in the intermediate layer is 100 wt%, wherein the propylene/1-butene random copolymer comprises 60 to 80 mol% of a unit derived from propylene and 20 to 40 mol% of a unit derived from 1-butene and has a melting point of 140°C or lower or a melting point that is not observed, the propylene polymer comprises 85 to 97 mol% of a unit derived from propylene and 3 to 15 mol% of a unit derived from C2-10 α-olefins excluding propylene and has a melting point of 120 to 170°C, crystalline polypropylene comprises 98 to 100 mol% of a unit derived from propylene and 0 to 2 mol% of C2-10 α-olefins excluding propylene and has a melting point of 150 to 170°C, and the 1-butene/α-olefin copolymer comprises 50 to 95 mol% of a unit derived from 1-butene and 50 to 5 mol% of a unit derived from C2-10 α-olefins excluding 1-butene. the crystalline polypropylene in an amount of 50 to 95 wt%, and the propylene/1-butene random copolymer in an amount of 50 to 5 wt%, provided that the total amount of and in the intermediate layer is 100 wt%, wherein the propylene/1-butene random copolymer comprises 60 to 80 mol% of a unit derived from propylene and 20 to 40 mol% of a unit derived from 1-butene and has a melting point of 140°C or lower or a melting point that is not observed, the propylene polymer comprises 85 to 97 mol% of a unit derived from propylene and 3 to 15 mol% of a unit derived from C2-10 α-olefins excluding propylene and has a melting point of 120 to 170°C, crystalline polypropylene comprises 98 to 100 mol% of a unit derived from propylene and 0 to 2 mol% of C2-10 α-olefins excluding propylene and has a melting point of 150 to 170°C, and the 1-butene/α-olefin copolymer comprises 50 to 95 mol% of a unit derived from 1-butene and 50 to 5 mol% of a unit derived from C2-10 α-olefins excluding 1-butene.