Duplex stainless steel (DSS) is an emerging construction material for structural engineering, which is featured with high mechanical strength and superior corrosion resistance. Compared with considerable research on DSS structural members, available research is relatively limited for structural joints/connections between these members. In line with this concern, this paper presents a comprehensive experimental and numerical study of duplex stainless steel bolted connections (DSSBCs), focusing on the behaviour and design related to block shear failure. Eleven specimens are tested to investigate the effect of different bolt arrangements on the block shear behaviour. Furthermore, a detailed numerical study was performed as a supplement to the experimental tests, where the anisotropic mechanical properties of DSS are considered in the finite element modelling. Based on the test and analysis results, it is found that the block shear failure mode of DSSBCs resembles that of carbon steel bolted connections, which can be characterised as necking of the tensile section and yielding of the shear sections. Using the experimental and numerical data obtained in this and previous studies, the applicability of various block shear design methods to stainless steel bolted connections is assessed. An updated design method is proposed for predicting the block shear capacity of duplex and austenitic stainless steel bolted connections. A proper partial safety factor/resistance factor is suggested for the proposed method based on the results of reliability analyses.