In this study, we investigated the influence of cold rolling reduction on microstructural evolution and slip behavior in Ta-10W alloy fabricated by vacuum arc melting (VAM). As the reduction increased, both single and multiple slips were observed within some grain interiors. At reductions of 20% and 40%, deformation bands, primarily consisting of γ-fiber components, formed within the grain interiors. The fraction of deformation bands (DBs) increased with higher reduction. Conversely, at 60% reduction, in addition to DBs, experimentally observed shear bands (SBs) with a herringbone pattern were formed. Both DBs and SBs predominantly formed in regions of concentrated strain (areas with high kernel average misorientation (KAM) and geometrically necessary dislocations (GND)). As the reduction increased, the misorientation angle between the matrix and the DBs or SBs gradually increased, while the width of the DBs decreased. To investigate the violation of Schmid’s law in Ta-10W alloy, slip trace and resolved shear stress (RSS) analyses were performed on observed slip lines within deformed grains. Contrary to conventional slips, where slip typically occurs on the plane with the highest RSS, slips in the Ta-10W alloy were confirmed to occur even on planes with lower RSS in certain grains. Hence, this study provides experimental evidence of Schmid’s law violation in Ta-10W alloy.