Custom Collection Initializers

No, the compiler requires a method named Add for the collection initializer to work. This is defined in C# specification and cannot be changed:

C# Language Specification - 7.5.10.3 Collection Initializers

The collection object to which a collection initializer is applied must be of a type that implements System.Collections.IEnumerable or a compile-time error occurs. For each specified element in order, the collection initializer invokes an Add method on the target object with the expression list of the element initializer as argument list, applying normal overload resolution for each invocation. Thus, the collection object must contain an applicable Add method for each element initializer. [emphasis mine]

Of course, the Add method can take more than one argument (like Dictionary<TKey, TValue>):

dic = new Dictionary<int, int> { 
    { 1, 2 },
    { 3, 4 }
};
// translated to:
dic = new Dictionary<int, int>();
dic.Add(1, 2);
dic.Add(3, 4);

Adding just as a sample answer of what works. AFAIK, only Add will work. Code snippet taken from Marius Schulz

// simple struct which represents a point in three-dimensional space
public struct Point3D
{
    public readonly double X;
    public readonly double Y;
    public readonly double Z;

    public Point3D(double x, double y, double z)
    {
        X = x;
        Y = y;
        Z = z;
    }
}

// implementation of a collection of points, which respects
// the compiler convention for collection initializers and
// therefore both implements IEnumerable<T> and provides
// a public Add method
public class Points : IEnumerable<Point3D>
{
    private readonly List<Point3D> _points;

    public Points()
    {
        _points = new List<Point3D>();
    }

    public void Add(double x, double y, double z)
    {
        _points.Add(new Point3D(x, y, z));
    }

    public IEnumerator<Point3D> GetEnumerator()
    {
        return _points.GetEnumerator();
    }

    IEnumerator IEnumerable.GetEnumerator()
    {
        return GetEnumerator();
    }
}

// instantiate the Points class and fill it with values like this:
var cube = new Points
{
    { -1, -1, -1 },
    { -1, -1,  1 },
    { -1,  1, -1 },
    { -1,  1,  1 },
    {  1, -1, -1 },
    {  1, -1,  1 },
    {  1,  1, -1 },
    {  1,  1,  1 }
};