The lack of information on trip purpose and alternative mode in micromobility service usage data remains a major analytical challenge. Conventional survey method is subject to significant sampling and stated preference biases. To overcome this challenge, this paper presents a new inference method through a case study of rental e-scooters in London. The inference method features a rule-based algorithm for matching observed rental e-scooter trips with filtered trip samples in the English National Travel Survey (NTS) series. Probability distribution of trip purposes and alternative modes are then retrieved from NTS. Inference results are validated using official data. Discrepancies, sources of biases and correction measures are investigated. Based on the inferred mode substitution pattern, we estimate greenhouse gas emissions reduction of selected rental e-scooter trips in London (36-103g CO2e per mile). It is expected that the proposed method is applicable to a wide range of micromobility studies using service usage data.