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Dental resin composites' performance is intricately linked to their polymerisation shrinkage characteristics. This study compares polymerisation shrinkage using advanced 3D micro-computed tomography (micro-CT) and traditional 2D linear assessments. It delves into the crucial role of filler content on shrinkage and the degree of conversion in dental resin composites, providing valuable insights for the field. Five experimental dental composite materials were prepared with increasing filler contents (55–75 wt%) and analysed using either 3D micro-CT for volumetric shrinkage or a custom-designed linometer for 2D linear shrinkage. The degree of conversion was assessed using Optical Photothermal Infrared (O-PTIR) and Fourier-Transform Infrared (FTIR) spectroscopy. Light transmittance through a 2-mm layer was evaluated using a NIST-calibrated spectrometer. Scanning Electron Microscopy (SEM) and Energy-Dispersive X-ray Spectroscopy (EDX) examined surface morphology and elemental distribution. Correlation between the investigated parameters was determined using Spearman correlation analyses. The study found significant differences in polymerisation-related properties among different filler content categories, with volumetric shrinkage consistently demonstrating higher mean values than linear shrinkage across most groups. Volumetric shrinkage decreased with increasing curing depth, showing no direct correlation between filler content and shrinkage levels at different curing depths. The results highlighted a strong negative correlation between filler content and degree of conversion, volumetric and linear shrinkage, as well as maximum shrinkage rate. Light transmittance showed a moderate correlation with the filler content and a weak correlation with other tested parameters. This study underscores the importance of considering both volumetric and linear shrinkage in the design and analysis of dental composite materials. The findings advocate optimising filler content to minimise shrinkage and enhance material performance. Integrating micro-CT and O-PTIR techniques offers novel insights into dental composites' polymerisation behaviour, providing a foundation for future research to develop materials with improved clinical outcomes. • 3D micro-CT and O-PTIR spectroscopy provide novel insights into dental composite polymerisation. • Filler content significantly influences polymerisation shrinkage and degree of conversion. • Volumetric shrinkage was consistently higher than linear shrinkage in most experimental groups. • Increasing filler content reduced shrinkage and improved material performance. • Integration of micro-CT and O-PTIR techniques advances understanding of dental composites. [ABSTRACT FROM AUTHOR]