This study investigates the anti-wetting behavior of liquid aluminum on microtextured QT700 cast iron surfaces for vacuum ladle applications. Periodic surface microstructures (micro-circular grooves, micro-pits, micro-grooves) are fabricated on QT700 substrates via nanosecond laser processing, with subsequent aluminum wetting dynamics analyzed at 900 °C using an advanced sessile drop apparatus equipped with high-speed imaging. Results demonstrate that all laser-generated microstructures inhibit aluminum wetting, exhibiting higher equilibrium contact angles compared to smooth surfaces. Micro-pit patterns show the most significant anti-wetting effect, achieving a maximum contact angle of 77°. Cross-sectional SEM-EDS analysis reveals vertical growth of intermetallic compounds at three-phase junctions, which mechanically pin the contact line through capillary force-induced reaction enhancement. Notably, the intermetallic layer thickness exceeds laser-ablated groove depth, resulting in similar final interface morphologies across textured and smooth surfaces. These findings provide mechanistic insights for designing non-wetting ladle linings through controlled interfacial reactions.