Background: Self-reported adherence to sling wear is unreliable due to recall bias. We aim to assess the feasibility and accuracy of quantifying sling wear and non-wear utilising slings pre-fitted with a GENEActiv accelerometer that houses triaxial acceleration and temperature sensors. Methods: Ten participants were asked to wear slings for 480 min (8 h) incorporating 180 min of non-wear time in durations varying from 5–120 min. GENEActiv devices were fitted in sutured inner sling pockets and participants logged sling donning and doffing times. An algorithm based on variability in acceleration in three axes and temperature change was developed to identify sling wear and non-wear and compared to participants’ logs. Results: There was no significant difference between algorithm detected non-wear duration (mean ± standard deviation = 172.0 ± 6.8 min/participant) and actual non-wear (179.7 ± 1.0 min/participant). Minute-by-minute agreement of sensor-detected wear and non-wear with participant reported wear was 97.3 ± 1.5% (range = 93.9–99.0), with mean sensitivity 94.3 ± 3.5% (range = 86.1–98.3) and specificity 99.1 ± 0.8% (range = 93.7–100). Conclusion: An algorithm based on accelerometer-assessed acceleration and temperature can accurately identify shoulder sling wear/non-wear times. This method may have potential for assessing whether sling wear adherence after shoulder surgeries have any bearing on patient functional outcomes.