The purpose of this paper is to analyze the Moore-Penrose pseudo-inversion of symmetric real matrices with application in the graph theory. We introduce a novel concept of positively and negatively pseudo-inverse matrices and graphs. We also give sufficient conditions on the elements of a block symmetric matrix yielding an explicit form of its Moore-Penrose pseudo-inversion. Using the explicit form of the pseudo-inverse matrix we can construct pseudo-inverse graphs for a class of graphs which are constructed from the original graph by adding pendent vertices or pendant paths.