First- and last-mile trips are becoming increasingly expensive and detrimental to the environment, especially within dense cities. Thus, new micro-mobility transportation modes such as e-scooter sharing systems have been introduced to fill the gaps in the transportation network. Furthermore, some recent studies examined e-scooters as a green option from the standpoint of environmental sustainability. Currently, e-scooter charging is conducted by competitive freelancers who do not consider the negative environmental impact resulting from not optimizing the fuel efficiency of their charging trips. Several disputes have been recorded among freelance chargers, especially when simultaneously arriving at an e-scooters location. The paper aims to find the optimal tours for all chargers to pick up e-scooters in the form of routes, such that each route contains one charger, and each e-scooter is visited only once by the set of routes, which are typically called an E-Scooter-Chargers Allocation (ESCA) solution. This study develops a mathematical model for the assignment of e-scooters to freelance chargers and adapts a simulated annealing metaheuristic to determine a near-optimal solution. We evaluated the proposed approach using real-world instances and a benchmark-simulated dataset. Moreover, we compare the proposed model benchmark dataset to the baseline (i.e., state-of-practice). The results show a reduction of approximately 61–79% in the total distance traveled, leading to shorter charging trips.