Thermo-acoustic (TA) ultrasound has attracted considerable interest during the last decade for its many advantages over the conventional electro-acoustic ultrasound. In this paper, a general expression of the acoustic pressure field of thermally induced ultrasonic emission from a spherical cavity surface is derived by using a fully thermally–mechanically coupled TA model. The characteristics and regularities of ultrasound from spherical focusing TA emitter can therefore be studied in detail. It is found that, for the TA emission in sphere shell, wideband flat amplitude–frequency response pattern, the most important feature of TA ultrasound in an open space from a technical standpoint, is seriously disrupted by wave interference occurring in spherical cavity. The dependences of sound pressure of TA ultrasound in spherical cavity on the heating frequency, the inner radius of spherical cavity, the location in spherical cavity, and the thickness of TA sample layer, as well as the type and filling pressure of gas in cavity are given and discussed. The currently used planar TA solution is only the special case for spherical cavity with infinite radius of the analytical solution developed in this work, which would be of significance for more comprehensive guide to understanding and using TA ultrasound.