The use of superaustenitic stainless steels (SASS) as an overlay replacement for nickel-based alloys can be an interesting alternative for the oil and gas industries, due to its lower cost, when compared to superalloys. Usually, the deposition is made with several welding passes by using conventional arc welding processes, such as gas tungsten arc welding (GTAW) or gas metal arc welding (GMAW) processes. In this respect, electro-slag welding (ESW), which promotes high heat inputs and low dilution of the welds, can also be attractive for this application, as it provides a higher productivity, once only one layer is needed for the deposition of the minimum thickness required. The present work evaluates the behavior of an AISI 904L SASS weld overlay deposited on a carbon steel ASTM A516 Grade 70 by ESW and GMAW processes. Both as-welded and heat-treated conditions were evaluated and compared. A multipass welding by GMAW process with three layers and 48 passes was performed on 12.5 × 200 × 250 mm steel plates with average welding energy of 1.0 kJ/mm. For ESW process, only one layer was deposited on 50 × 400 × 400 mm steel plates with average welding energy of 11.7 kJ/mm. After welding, a post-weld heat treatment (PWHT) at 620 °C for 10 h was performed in half of the steel plate, in order to allow the comparison between this condition and the as-welded one. For both processes, the austenitic microstructure of the weld deposits was characterized by optical microscopy and scanning electron microscopy with electron backscatter diffraction. A low proportion of secondary phases were observed in all conditions, and the PWHT did not promote significant changes on the hardness profile. Martensite for GMAW process and bainite for ESW process were the microstructural constituents observed at the coarse grain heat-affected zone, due to the different cooling rates. For ESW process, no evidences of partially diluted zones were found. As a consequence of the microstructural findings, the hardness results for ESW were lower than those usually observed for other electric arc welding processes. In addition, specimens subject to bending tests performed in accordance with the current standards used for qualification of welding procedures were approved. These evidences allow the conclusion that the ESW process can provide deposits with high quality despite the high welding energy levels, in order to achieve the desired productivity, being an interesting alternative for AISI 904L weld overlays.