I've tried to make a portable way of ensuring endian-specific code gets generated at compile time using C++11, however I only have a computer with Windows on it to test at the moment. Because of this, I'm a bit limited in the amount of places where I can test my code. Also, would anyone be able to offer some best-practices or tips different ways to improve this? My intention is to use this in a small math library where serialization is a pretty high priority.

The function itself is fairly simple. It checks the values of an array for whichever byte comes first. It then returns a constant value, representing the target machine's endianness, through an enumeration. If everything works correctly, then this code can replace any runtime checks that either I or anyone else uses for endian checking.

/* 
 * A simple compile-time endian test
 * g++ -std=c++11 -Wall -Werror -Wextra -pedantic -pedantic-errors endian.cpp -o endian
 *
 * This can be used with specialized template functions, classes, and class
 * methods in order better tailor code and reduce reliance on runtime
 * checking systems.
 */

#include <cstdint>
#include <iostream>

/**
 * hl_endianness
 *
 * This enumeration can be placed into templated objects in order to generate
 * compile-time code based on a program's target endianness.
 *
 * The values placed in this enum are used just in case the need arises in
 * order to manually compare them against the number order in the
 * endianValues[] array.
 */
enum hl_endianness : uint32_t {
    HL_LITTLE_ENDIAN   = 0x03020100,
    HL_BIG_ENDIAN      = 0x00010203,
    HL_PDP_ENDIAN      = 0x01000302,
    HL_UNKNOWN_ENDIAN  = 0xFFFFFFFF
};

/**
 * A constant array used to determine a program's target endianness. The
 * values
 *  in this array can be compared against the values placed in the
 * hl_endianness enumeration.
 */
static constexpr uint8_t endianValues[4] = {0, 1, 2, 3};

/**
 * A simple function that can be used to help determine a program's endianness
 * at compile-time.
 */
constexpr hl_endianness getEndianOrder() {
    return
        (0x00 == endianValues[0])           // If Little Endian Byte Order,
            ? HL_LITTLE_ENDIAN              // return 0 for little endian.
            : (0x03 == endianValues[0])     // Else if Big Endian Byte Order,
                ? HL_BIG_ENDIAN             // return 1 for big endian.
                : (0x02 == endianValues[0]) // Else if PDP Endian Byte Order,
                    ? HL_PDP_ENDIAN         // return 2 for pdp endian.
                    : HL_UNKNOWN_ENDIAN;    // Else return -1 for wtf endian.
}

#define HL_ENDIANNESS getEndianOrder()

/*
 * Test program
 */
int main() {
    #if defined _WIN32 || defined _WIN64
        static_assert(
            HL_ENDIANNESS == HL_LITTLE_ENDIAN,
            "Aren't Windows programs Little-Endian?"
        );
    #endif

    constexpr hl_endianness endianness = HL_ENDIANNESS;
    
    std::cout << "This machine is: ";
    
    switch (endianness) {
        case HL_LITTLE_ENDIAN:
            std::cout << "LITTLE";
            break;
        case HL_BIG_ENDIAN:
            std::cout << "BIG";
            break;
        case HL_PDP_ENDIAN:
            std::cout << "PDP";
            break;
        case HL_UNKNOWN_ENDIAN:
        default:
            std::cout << "UNKNOWN";
    }
    
    std::cout << " endian" << std::endl;
}

Edit:

I can try dereferencing the pointer offset to the endianValues array but I'm still not sure if it will end up defaulting to 0 (the first explicitly set value in the array).

constexpr hl_endianness getEndianOrder() {
    return
        (0x00 == *endianValues)           // If Little Endian Byte Order,
            ? HL_LITTLE_ENDIAN              // return 0 for little endian.
            : (0x03 == *endianValues)     // Else if Big Endian Byte Order,
                ? HL_BIG_ENDIAN             // return 1 for big endian.
                : (0x02 == *endianValues) // Else if PDP Endian Byte Order,
                    ? HL_PDP_ENDIAN         // return 2 for pdp endian.
                    : HL_UNKNOWN_ENDIAN;    // Else return -1 for wtf endian.
}