Fibromyalgia syndrome (FMS) is a common condition lacking strong diagnostic criteria; these criteria continue to evolve as more and more studies are performed to explore it. This investigation sought to identify whether participants with FMS have more frequent and larger postural/spinal displacements in comparison to a matched control group without the condition of FMS. A total of 67 adults (55 females) out of 380 participants with FMS were recruited. Participants with FMS were sex- and age-matched with 67 asymptomatic participants (controls) without FMS. We used a three-dimensional (3D) postural assessment device (Formetric system) to analyze five posture variables in each participant in both groups: (1) thoracic kyphotic angle, (2) trunk imbalance, (3) trunk inclination, (4) lumbar lordotic angle, and (5) vertebral rotation. In order to determine whether 3D postural measures could predict the likelihood of a participant having FMS, we applied the matched-pairs binary logistic regression analysis. The 3D posture measures identified statistically and clinically significant differences between the FMS and control groups for each of the five posture variables measured (p < 0.001). For three out of five posture measurements assessed, the binary logistic regression identified there was an increased probability of having FMS with an increased: (1) thoracic kyphotic angle proportional odds ratio [Prop OR] = 1.76 (95% CI = 1.03, 3.02); (2) sagittal imbalance Prop OR = 1.54 (95% CI = 0.973, 2.459); and (3) surface rotation Prop OR = 7.9 (95% CI = 1.494, 41.97). We identified no significant probability of having FMS for the following two postural measurements: (1) coronal balance (p = 0.50) and (2) lumbar lordotic angle (p = 0.10). Our study’s findings suggest there is a strong relationship between 3D spinal misalignment and the diagnosis of FMS. In fact, our results support that thoracic kyphotic angle, sagittal imbalance, and surface rotation are predictors of having FMS.