Very few porous low-k dielectric materials meet the basic requirements for integration into the back end of the line (BEOL) metallization. According to the International Technology Roadmap for Semiconductors, 2005, candidates for the 45 nm node need a k<2.2 and a minimum adhesion strength of 5 J/m2. Recently, a low-k dielectric material was developed, called nano-clustered silica (NCS). It is a spin-on glass with k<2.3. NCS is constitutively porous, with a micro- and mesopore size of ~2.8 nm. The first reported adhesion strength of this material was 10+ J/m2. We investigated the nature of the adhesive strength of NCS by critical and sub-critical fracture and Fourier Transform IR Spectroscopy (FTIR). The four-point bend technique and a mixed-mode double cantilever beam technique were employed. The sub-critical crack growth studies were performed in humid environments and ambient temperatures. Different post-treatments were used on NCS to achieve different molecular structure, as measured with FTIR. A correlation between molecular structure and critical adhesion energy was found. Atomistic parameters were calculated from the sub-critical crack growth data. A dependency of fracture behavior on post-treatment and, therefore, structure was observed.