Differences in fibromyalgia impact on functioning exist and appear to be influenced by numerous factors, including symptomatology severity, as well as the cognitive profile of the individual. The contribution of these elements, however, tends to be explored in a fragmented manner. To address this issue, we tested a comprehensive structural equation model in which associations of cognitive fusion and pain catastrophizing with function limitations are investigated through fibromyalgia symptomatology (i.e., fatigue, pain severity, and depression) in 231 women with fibromyalgia. In the model, cognitive fusion and two catastrophizing components (magnification and helplessness) were associated with poorer functioning indirectly through fibromyalgia symptomatology. Only the rumination component of catastrophizing had a direct association with functional limitations. All fibromyalgia symptoms were linked to increased functional limitations. A parsimonious model with significant associations only obtained an excellent fit (S-B χ2 = 774.191, df = 543, p < 0.001; CFI = 0.943; RMSEA = 0.043; CAIC = −2724.04) and accounted for 50% of the variance of functional limitations. These results suggest that the relationship between psychological cognitive processes, fibromyalgia symptomatology, and functional limitations is complex and support the need for comprehensive models such as the present. The findings are discussed in the context of personalized psychological treatments (i.e., the need to address certain cognitive processes according to the problematic symptomatology or outcome).