Abstract: Dissimilar welding of the Ti–6Al–4V (Ti-6-4) to Ti–6A1–6V–2Sn (Ti-6-6-2) alloys was performed by CO2 laser in this work. The effect of post-weld heat treatment (PWHT) on the notched tensile strength (NTS) of the dissimilar weld was evaluated. Moreover, the results were also compared with the homogeneous laser welds with the same PWHT. Similar to the Ti-6-4 welds, the NTS of the FZ for dissimilar welds was less sensitive to PWHT conditions; the NTS of the FZ for distinct dissimilar welds fell within the range of 1060–1180 MPa. The results indicated a minor rise in the Mo equivalent of the titanium alloy promoted the formation of fine α + β microstructures in the form of basket weave in the welds, which resulted in high hardness accompanied with low NTS of the welds.