National libraries play a vital role in preserving cultural heritage, fostering literacy, and providing equitable access to information. Despite this mandate, user uptake of Kenya National Library Services (KNLS) has been declining, raising concerns among stakeholders. This study assessed the relationship between structural alignment and users’ uptake of KNLS services. Anchored on the Resource-Based View theory, the study adopted a correlational research design and was conducted at the KNLS head office in Nairobi County, targeting 225 employees across departments. A sample of 144 respondents was determined using the Yamane formula and selected through stratified and simple random sampling. Data was collected using structured questionnaires, with reliability confirmed through Cronbach’s alpha coefficient (α = 0.852). Descriptive analysis employed means and standard deviations, while correlation and regression analysis tested the hypotheses. The findings revealed a moderate positive correlation between structural alignment and user uptake (r = 0.427), although regression analysis indicated that structural alignment (β = 0.411, p > 0.05) was not a statistically significant predictor. The model accounted for 36.5% of the variation in users’ uptake, suggesting that structural alignment alone does not directly predict service utilization but contributes indirectly by creating an enabling organizational environment. The study concludes that enhancing centralization, formalization, and departmentalization within KNLS could improve interdepartmental coordination and service delivery. It recommends embedding structural optimization metrics into KNLS policies to strengthen responsiveness and user engagement. These findings are valuable to KNLS management, policymakers, and scholars interested in organizational alignment and service delivery.