The objective of this research was to analyze pedestrian exposure to risk along urban trips in relation to pedestrian crossing behavior. First, an appropriate microscopic indicator was selected for the estimation of pedestrian exposure to risk while a person crossed a road at isolated locations. This indicator expressed exposure as the number of vehicles encountered by pedestrians during the crossing of a single uncontrolled road lane and could be further adapted and applied for various road design and traffic control features. Moreover, the number and type of crossings along a pedestrian trip could be identified on the basis of the trip length and topology, whereas the set of choices of alternative crossing locations for each crossing decision could also be defined. The crossing probability associated with each alternative location along the trip could then be estimated by means of a sequential logit model. A method is presented for the estimation of exposure to risk for pedestrians along a trip in relation to their crossing behavior. The proposed approach was demonstrated in a pilot implementation for a typical pedestrian trip in the center of Athens, Greece, for four scenarios combining different traffic conditions and pedestrian walking speed. The results showed that exposure to risk for pedestrians along a trip was significantly affected by the pedestrians’ crossing choices, as well as by road and traffic characteristics. Results also revealed that pedestrians with increased walking speed might have partly compensated for their exposure to risk so that the risk was not significantly affected by traffic volume. Moreover, specific locations with increased pedestrian exposure to risk could be identified for each trip. The proposed microscopic analysis of exposure to risk proved advantageous compared with existing macroscopic ones. This microscopic analysis revealed the different possible definitions and aspects of pedestrian exposure, with useful implications for road safety analysis.