Climate change patterns and expected extreme weather conditions drive urban design practices toward more effective adaptation strategies for the built environment. Biskra City, one of the largest urban areas in the Algerian Sahara territory, has suffered from unprecedented extreme weather patterns, specifically during the summer. This paper examined outdoor thermal comfort in the arid climates of Biskra, Algeria, during summer extreme conditions by investigating the impact of the height-to-width (H/W) ratio aspect and the north–south (N-S) and east–west (E-W) street orientations on pedestrian thermal comfort with the parameterization of external building envelopes using brick, concrete, adobe, and limestone materials. This study was conducted with ENVI-met 5.1.1 software, based on 24 parametric scenarios, to identify the most effective composition for outdoor thermal stress mitigation using the physiological equivalent temperature (PET) thermal index. Across all scenarios, the PET index values fluctuated between PETmin = 32.2 °C and PETmax = 60.6 °C at different hours. The coupling between the H/W ratio and street orientation as geometry factors and building envelope characteristics reveals six distinct categories of building materials, each with an impact on outdoor thermal comfort: (1) high cooling (60–100%), (2) medium cooling (40–60%), (3) low cooling (<40%), (4) high heating (60–100%), (5) medium heating (40–60%), and (6) low heating material (<40%). Therefore, in the N-S orientation, limestone walls can provide a cooling efficiency range from 85% to 100% throughout deep and shallow canyons. Contrary to this, brick walls can cause a heat retention range varying from 70% to 93% within the same canyons. When considering extreme summer conditions in arid climates, the results show that the most effective bioclimatic passive strategy that could be achieved is the E-W orientation, within H/W < 1, characterized by a high albedo building material.