High-efficiency submegahertz bandwidth photon pair generators will enable the field of quantum technology to transition from laboratory demonstrations to transformational applications involving information transfer from photons to atoms. While spontaneous parametric processes are able to achieve high-efficiency photon pair generation, the spectral bandwidth tends to be relatively large, as defined by phase-matching constraints. To solve this fundamental limitation, we use an ultrahigh quality factor (Q) fused silica microsphere resonant cavity to form a photon pair generator. We present the full theory for the spontaneous four-wave mixing (SFWM) process in these devices, fully taking into account all relevant source characteristics in our experiments. The exceptionally narrow (down to kilohertz-scale) linewidths of these devices result in a reduction in the bandwidth of the photon pair generation, allowing submegahertz spectral bandwidth to be achieved. Specifically, using a pump source centered around 1550 nm, photon pairs with the signal and idler modes at wavelengths close to 1540 and 1560 nm, respectively, are demonstrated. We herald a single idler-mode photon by detecting the corresponding signal photon, filtered via transmission through a wavelength division multiplexing channel of choice. We demonstrate the extraction of the spectral profile of a single peak in the single-photon frequency comb from a measurement of the signal–idler time of emission distribution. These improvements in device design and experimental methods enabled the narrowest spectral width (Δν=366kHz) to date in a heralded single-photon source based on SFWM.