Wearable devices are increasingly utilized to monitor physical activity and sedentary behaviors. Accurately determining wear/non-wear time is complicated by zero counts, where the acceleration-based indexes do not estimate activity intensity, often leading to misclassifications. We propose a novel synthetic classification algorithm that leverages both the probability and continuity of zero counts, aiming to enhance the accuracy of activity estimation. The physical activity data were obtained from 12 office workers wearing wearable devices with 3-axis accelerometers. The wear/non-wear times are classified by the commonly used current method (zero counts lasting longer than 60 minutes are classified as non-wear) and the proposed method. In the proposed method, only times that satisfy the following two criteria are classified as the wear time. (1) The appearance probability preceding and following 60 minutes must be less than the threshold value. (2) The number of consecutive zeros must be less than 10 minutes. The effectiveness of both the current and proposed classification methods was evaluated against the actual behavioral records. This evaluation utilized simulation-based augmented data, which was implemented to address the limited variability inherent in the original dataset. The range of recall, specificity, precisions, and accuracy classified by the current method were 0.93-1.00, 0.93-0.96, 0.85-0.88, and 0.94-0.97, respectively. Indeed, the proposed method shows 0.95-1.00, 0.99-1.00, 0.97-1.00, and 0.98-1.00, respectively. The reduction of misclassification of non-wear time as wear time was achieved by the synthetic classification algorithm. The performance of the proposed approach showed accurate classification of the wear/non-wear time of wearable sensors in office workers.