Mass light-rail transit (LRT) has been promoted as an effective solution toward sustainable transportation in urban areas. This paper presents a micro-simulation framework combining the multi-state supernetwork (MSN) approach and a mobility-related emission module to evaluate the mobility and environmental effects of LRT developments. The evaluation framework considers individuals’ mode choice of LRT and particularly the trip chaining with their private vehicles to conduct daily activity programs. As complementary policies to LRT developments, parking pricing and park & ride (P + R) developments are also integrated. The output of daily travel patterns from the MSN approach can be used congruently to calculate the air pollutant emissions. The framework is applied to the extended Metropolitan area of Eindhoven (the Netherlands), where new LRT developments and additional parking policies are considered to improve accessibility and reduce environmental effects. The micro-simulation concerns a synthetic population of approximately 110,000 individuals and seven LRT scenarios. The simulation results show a decrease in overall vehicle kilometers traveled and travel time, an increase in public transport use, a decrease in total air pollutant emissions, and an increase in activities in areas around public transport stops and P + R locations. It appears that the inclusion of parking measures in the simulations strengthens the effects, confirming the effectiveness of policy combinations.