Positive ions species resulting from photon-stimulated desorption (PSD) and photolysis from B10H14 at solid surfaces have been determined by means of time-of-flight mass spectroscopy using single-bunch operation of synchrotron radiation (SR) (h nu greater than or equal to 100 eV). The ionic species desorbing from molecularly adsorbed B10H14 on Si(100) are H-2(+), BH2+, BH3+, and B2H4+. During SR excited chemical vapor deposition (SR-CVD) of boron films, the primary ion products created by photolysis of B10H14 are H-2(+), B10Hx+, BHx+, and B9Hx+. From the boron films deposited by SR-CVD, the additional PSD of B2H3+ and B2H5+ is observed and indicates that the boron film surface is terminated by several kinds of higher-order boron hydrides. The formation of BH3+ and B2H4+ is initiated by bulk-mediated secondary processes, whereas the formation of H-2(+) and B10Hx+ is a direct consequence of photoabsorption. The pressure dependence of the intensities of the ion species can be used to distinguish their gas and surface origins.