This study investigated the complex thermal accumulation characteristics and their effects in the time and spatial domains during the preparation of complex Nitinol (NiTi) alloy structures using laser powder bed fusion (LPBF) technology. The findings reveal a pronounced size dependency phenomenon when the formed dimensions fall below 2 mm. Specifically, a reduction in formed size leads to a marked surge in element loss, a heightened prevalence of internal defects, and a corresponding decline in both mechanical and functional properties. Small-sized (<0.5 mm) samples have significant thermal accumulation due to their fast heating and slow cooling rates, requiring control of heat input. Medium sized (0.5–2 mm) samples have significant temperature gradients as a result of their rapid heating and cooling rates, requiring control of high-temperature residence time. Large sized (> 2 mm) samples necessitate the insulation measures to reduce thermal stress, owing to their sluggish heating and rapid cooling characteristics. Therefore, we developed a model to evaluate the thermal history characteristics of parameters or design schemes and compensate or eliminate heat accumulation during the machining process to balance the thermal history characteristics. This model can also be combined with a thermal field detection system to develop real-time thermal management and control modules for processing. The key to eliminating size-dependency effects is to homogenize the microstructure. A single aging heat treatment (773 K for 0.5 h with air cooling) can effectively homogenize the structure and eliminate size dependence.