In this study, thermal deformation in non-planar, large-scale additive manufacturing (LSAM) was experimentally and numerically investigated. A Bézier-based non-planar build surface was fabricated by CNC machining, and a single layer of ABS was deposited using a hybrid LSAM system. Toolpaths with raster angles of 0° and 45° were generated for surface-conformal printing. Infrared thermography was employed to monitor the thermal history during deposition. A three-dimensional finite element model was developed to simulate transient heat transfer and thermally induced deformation. Experimental deformation was quantified by 3D scanning and compared with simulation results. The results show that the slope geometry strongly influences deformation direction: negative slopes promote contraction, whereas positive slopes lead to upward deflection. Maintaining the material temperature above the glass transition temperature significantly reduces skew deformation. The finite element method predictions demonstrate strong agreement with experimental measurements, with normalized root mean square errors (NRMSEs) of approximately 11% for thermal deformation and 10% for temperature history. The proposed framework enables prediction and mitigation of thermal warping in non-planar polymer additive manufacturing.