Biocomposite films based on PLA reinforced with different β-TCP contents (10%, 20%, and 25%wt.) were fabricated via solvent casting and immersed in SBF for 7, 14, and 21 days. The bioactivity, morphological, and thermal behavior of composites with immersion were studied using scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) microanalysis, weight loss (WL), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and gel permeation chromatography (GPC). This broad analysis leads to a deeper understanding of the evolution of the polymer–filler interaction with the degradation of the biocomposites. The results showed that β-TCP gradually evolved into carbonated hydroxyapatite as the immersion time increased. This evolution affected the interaction of β-TCP with PLA. PLA and β-TCP interactions differed from PLA and carbonated hydroxyapatite interactions. It was observed that β-TCP inhibited PLA hydrolysis but accelerated the thermal degradation of the polymer. β-TCP retarded the cold crystallization of PLA and hindered its crystallinity. However, after immersion in SBF, particles accelerated the cold crystallization of PLA. Therefore, considering the evolution of β-TCP with immersion in SBF is crucial for an accurate analysis of the biocomposites’ degradation. These findings enhance the comprehension of the degradation mechanism in PLA/β-TCP, which is valuable for predicting the degradation performance of PLA/β-TCP in medical applications.