X(2)(-)(H(2)O) [X = O, F] is utilized to explore water binding motifs to an excess electron via ab initio calculations at the MP4(SDQ)/aug-cc-pVDZ + diffs(2s2p,2s2p) level of theory. X(2)(-)(H(2)O) can be regarded as a water molecule that binds to an excess electron, the distribution of which is gauged by X(2). By varying the interatomic distance of X(2), r(X1-X2), the distribution of the excess electron is altered, and the water binding motifs to the excess electron is then examined. Depending on r(X1-X2), both binding motifs of C(s) and C(2v) forms are found with a critical distance of ∼1.37 Å and ∼1.71 Å for O(2)(-)(H(2)O) and F(2)(-)(H(2)O), respectively. The energetic and geometrical features of O(2)(-)(H(2)O) and F(2)(-)(H(2)O) are compared. In addition, various electronic properties of X(2)(-)(H(2)O) are examined. For both O(2)(-)(H(2)O) and F(2)(-)(H(2)O), the C(s) binding motif appears to prevail at a compact distribution of the excess electron. However, when the electron is diffuse, characterized by the radius of gyration in the direction of the X(2) bond axis with a threshold of ∼0.84 Å, the C(2v) binding motif is formed.