The paper investigates the arc behavior and molten metal flow during Keyhole tungsten inert gas (K-TIG) welding of dissimilar materials, Invar 36 and stainless steel (types 304, 316, 309, and 310) specifically. A high-speed camera was used to capture the contour of the molten pool in real time. Results showed that in stainless steel welding, the arc shape is bell-shaped, and the distance from the tip of the molten pool to the keyhole decreases with increasing thermal conductivity (6.76–10.86 mm). When Invar 36 was butt-welded, the arc contracted. However, when Invar 36 was welded with dissimilar materials of stainless steel, the arc deflected to the Invar 36 side. The deflection angle ranged from 29.9° to 37°, resulting in an asymmetric arc shape. The distance from the tip of the molten pool to the keyhole increased to 10.88–13.33 mm, which was about 42% higher than that of the same material welding. Metallographic analysis showed that the width of the heat affected zone on the Invar 36 side increases with the decrease in thermal conductivity of the stainless steel (1.77–2.03 mm). Differences in thermophysical properties and viscosity further led to asymmetric molten pool flow and metal accumulation behavior. This study quantified the formation mechanism of arc deflection and weld pool asymmetry in K-TIG welding of dissimilar materials.