Climate change and the associated increase in heat-related hazards pose a pressing threat to urban residents’ health and well-being. People, when walking in particular, are at risk of experiencing heat stress as they navigate urban environments. This study proposes a novel heat risk assessment framework combining pedestrian mobility modeling with urban microclimate modeling. Using this framework, we assessed pedestrian heat-related exposure and risk in urban areas by integrating the Universal Thermal Climate Index (UTCI) as the hazard and pedestrian trips to critical destinations as exposure. We considered temporal variation, in both hazard and exposure, by examining different time periods during the day—morning peak, midday, and evening peak. In addition to hazard and exposure, we also considered vulnerability by focusing on young children and older adults. We contribute to improving the spatial resolution of heat risk assessment by analyzing the hazard for pedestrian trips between home locations and five critical destinations—bus stops, rail stations, parks, schools, and commercial amenities—at the address-point level and using a pedestrian network comprising sidewalks and crosswalks. Our framework helps identify sidewalks with high heat exposure levels as well as home locations with high cumulative heat risk, accounting for walking trips to critical destinations along feasible routes. We demonstrated the effectiveness of this framework by applying it to a 36-square-kilometer area of central Los Angeles, CA. Our findings offer valuable information to urban planners and policy-makers, supporting evidence-based prioritization of intervention sites, climate adaptation strategies, and policy decisions essential for climate-proof planning. By implementing targeted interventions in areas where heat hazard is expected to affect the most vulnerable pedestrians, planners can create heat-resilient, pedestrian-friendly environments while prioritizing the health and well-being of vulnerable groups. This study contributes to the growing knowledge of robust risk assessment methodologies for climate-proof planning, specifically with regard to addressing outdoor heat-related risks during extreme heat events.