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In thick section laser welding, filler metal addition is usually required to improve joint fit-up tolerances or to control the chemical composition of the weld metal. With deep and narrow welds produced using an over-alloyed filler metal, it may be challenging to ensure that the filler metal and its elements are homogeneously mixed and evenly distributed throughout the fusion zone. Inhomogeneous filler metal mixing can cause unfavourable changes to weld metal chemistry and microstructure. Filler metal mixing behaviour in laser-arc hybrid and laser cold-wire welding is studied in this work. Welding tests were conducted on 10 mm thick butt-welded joints of AISI 316L austenitic stainless steel. An overmatching type 2205 duplex stainless steel filler wire was used to obtain a composition contrast between the base metal and filler metal. Energy dispersive spectroscopy (EDS) with chromium as the trace element was used for element mapping and stepwise characterization of the weld cross-section samples. Optical metallography was used to observe possible inhomogeneous filler metal mixing behaviour like local acute changes in macro- and microstructural features. The results showed a clear difference in filler metal mixing between the weld surface part (upper half) of the weld and the weld root part (lower half) in 10 mm thick welded cross-sections for closed root gap of I-groove welds or when the gap was only 0.4 mm. In narrow I-groove preparations, inhomogeneous mixing phenomena were more pronounced in laser cold-wire welds than in laser-arc hybrid welds. In both welding processes, a combination of trailing wire feeding and the use of a wider groove enabled filler metal to be introduced deeper into the bottom of the groove and improved mixing in the root portion of the welds.