Respiratory rate (RR) is a key parameter used in healthcare for monitoring and predicting patient deterioration. However, continuous and automatic estimation of this parameter from wearable sensors is still a challenging task. Various methods have been proposed to estimate RR from wearable sensors using windowed segments of the data; e.g., often using a minimum of 32 s. Little research has been reported in the literature concerning the instantaneous detection of respiratory rate from such sources. In this paper, we develop and evaluate a method to estimate instantaneous respiratory rate (IRR) from body-worn reflectance photoplethysmography (PPG) sensors. The proposed method relies on a nonlinear time-frequency representation, termed the wavelet synchrosqueezed transform (WSST). We apply the latter to derived modulations of the PPG that arise from the act of breathing.We validate the proposed algorithm using (i) a custom device with a PPG probe placed on various body positions and (ii) a commercial wrist-worn device (WaveletHealth Inc., Mountain View, CA, USA). Comparator reference data were obtained via a thermocouple placed under the nostrils, providing ground-truth information concerning respiration cycles. Tracking instantaneous frequencies was performed in the joint time-frequency spectrum of the (4 Hz re-sampled) respiratory-induced modulation using the WSST, from data obtained from 10 healthy subjects. The estimated instantaneous respiratory rates have shown to be highly correlated with breath-by-breath variations derived from the reference signals. The proposed method produced more accurate results compared to averaged RR obtained using 32 s windows investigated with overlap between successive windows of (i) zero and (ii) 28 s. For a set of five healthy subjects, the averaged similarity between reference RR and instantaneous RR, given by the longest common subsequence (LCSS) algorithm, was calculated as 0.69; this compares with averaged similarity of 0.49 using 32 s windows with 28 s overlap between successive windows. The results provide insight into estimation of IRR and show that upper body positions produced PPG signals from which a better respiration signal was extracted than for other body locations.