Although Big5 and CP950 are almost the same there are differences. On the Unicode website there are reference files for converting different encodings to Unicode, you will see that Big5 and CP950 are different. My experience of Iconv has been good - I suspect its behavior may be correct.
Some of the characters found in CP950 but not Big5 have the hex values: 0x00, 0x01, 0x02, 0x03, 0x04, 0x05, 0x06, 0x07, 0x08, 0x09, 0x0A, 0x0B, 0x0C, 0x0D, 0x0E, 0x0F, 0x10, 0x11, 0x12, 0x13, 0x14, 0x15, 0x16, 0x17, 0x18, 0x19, 0x1A, 0x1B, 0x1C, 0x1D, 0x1E, 0x1F, 0x20, 0x21, 0x22, 0x23, 0x24, 0x25, 0x26, 0x27, 0x28, 0x29, 0x2A, 0x2B, 0x2C, 0x2D, 0x2E, 0x2F, 0x30, 0x31, 0x32, 0x33, 0x34, 0x35, 0x36, 0x37, 0x38, 0x39, 0x3A, 0x3B, 0x3C, 0x3D, 0x3E, 0x3F, 0x40, 0x41, 0x42, 0x43, 0x44, 0x45, 0x46, 0x47, 0x48, 0x49, 0x4A, 0x4B, 0x4C, 0x4D, 0x4E, 0x4F, 0x50, 0x51, 0x52, 0x53, 0x54, 0x55, 0x56, 0x57, 0x58, 0x59, 0x5A, 0x5B, 0x5C, 0x5D, 0x5E, 0x5F, 0x60, 0x61, 0x62, 0x63, 0x64, 0x65, 0x66, 0x67, 0x68, 0x69, 0x6A, 0x6B, 0x6C, 0x6D, 0x6E, 0x6F, 0x70, 0x71, 0x72, 0x73, 0x74, 0x75, 0x76, 0x77, 0x78, 0x79, 0x7A, 0x7B, 0x7C, 0x7D, 0x7E, 0x7F, 0x80, 0x81, 0x82, 0x83, 0x84, 0x85, 0x86, 0x87, 0x88, 0x89, 0x8A, 0x8B, 0x8C, 0x8D, 0x8E, 0x8F, 0x90, 0x91, 0x92, 0x93, 0x94, 0x95, 0x96, 0x97, 0x98, 0x99, 0x9A, 0x9B, 0x9C, 0x9D, 0x9E, 0x9F, 0xA0, 0xA1, 0xA15A, 0xA1C3, 0xA1C5, 0xA1FE, 0xA240, 0xA3E1, 0xA2CC, 0xA2CE
. If any of your input contains these values, then the file is not valid Big5.