In modern C++11 or later (as your question was originally tagged C++ only) you have what is called aggregate initialization. It works like this:
struct test_str {
unsigned char Add[6];
unsigned int d;
unsigned char c;
} my_str { {0x11, 0x22, 0x33, 0x44, 0x55, 0x66},
0xffe,
10
};
int main()
{}
Live on Coliru
The inner pair of braces is not really necessary, but I prefer it for the sake of clarity.
PS: you should get your hands on a good introductory C++ book so you learn the basics of the language.
EDIT
In C (as you re-tagged your question) and pre C++11, you need an equal sign. Furthermore, in C the inner braces are not optional:
struct test_str {
unsigned char Add[6];
unsigned int d;
unsigned char c;
} my_str = { {0x11, 0x22, 0x33, 0x44, 0x55, 0x66},
0xffe,
10
};
int main()
{}