First make sure you have a binary image. If you have a gray scale image, do this first
binaryImage = grayImage > 128;
Then call imclearborder() and bwboundaries()
binaryImage = imclearborder(binaryImage);
boundaries = bwboundaries(binaryImage);
x = boundaries{1}(:, 2);
y = boundaries{1}(:, 1);
hold on;
plot(x, y, 'r-', 'LineWidth', 2);