Exposure to natural vegetation (ie, "greenspace") is related to beneficial outcomes, including higher positive and lower negative affect, in individuals with and those without mental health concerns. Researchers have yet to examine dynamic associations between greenspace exposure and affect within individuals over time. Smartphone-based ecological momentary assessment (EMA) and passive sensors (eg, GPS, microphone) allow for frequent sampling of data that may reveal potential moment-to-moment mechanisms through which greenspace exposure impacts mental health. In this study, we examined associations between greenspace exposure and affect (both self-reported and inferred through speech) in people with and those without schizophrenia spectrum disorder (SSD) at the daily level using smartphones. Twenty people with SSD and 14 healthy controls reported on their current affect 3 times per day over 7 days using smartphone-based EMA. Affect expressed through speech was labeled from ambient audio data collected via the phone's microphone using Linguistic Inquiry and Word Count (LIWC). Greenspace exposure, defined as the normalized difference vegetation index (NDVI), was quantified based on continuous geo-location data collected from the phone's GPS. Overall, people with SSD used significantly more positive affect words (P=.04) and fewer anger words (P=.04) than controls. Groups did not significantly differ in mean EMA-reported positive or negative affect, LIWC total word count, or NDVI exposure. Greater greenspace exposure showed small to moderate associations with lower EMA-reported negative affect across groups. In controls, greenspace exposure on a given day was associated with significantly lower EMA-reported anxiety on that day (b=-0.40, P=.03, 95% CI -0.76 to -0.04) but significantly higher use of negative affect words (b=0.66, P<.001, 95% CI 0.29-1.04). There were no significant associations between greenspace exposure and affect at the daily level among participants with SSD. Our findings speak to the utility of passive and active smartphone assessments for identifying potential mechanisms through which greenspace exposure influences mental health. We identified preliminary evidence that greenspace exposure could be associated with improved mental health by reducing experiences of negative affect. Future directions will focus on furthering our understanding of the relationship between greenspace exposure and affect on individuals with and those without SSD.