Photometric and spectroscopic analysis of high Galactic latitude molecular clouds. I - Distances and extinctions of stars toward 25 selected regions The paper presents new photoelectric photometry in the UBV, uvby, andH-beta systems for 320 stars at high Galactic latitudes, selected fortheir proximity to the densest portions of a variety of high Galacticlatitude atomic and molecular clouds. Low-resolution digital spectra areemployed to classify 115 of the stars. Several novel techniques aredeveloped for automatic digital spectral classification, and fordereddening Stromgren uvby-beta and Johnson UBV,H-beta photometry. Anempirical determination of the errors in the derived dereddened colors,and techniques for converting between the two photometric systems arepresented on the basis of the analysis of a statistically significantsample of 1480 stars with complete data sets in both photometric systemsand with an accurate MK spectral type. New constraints on the distancesto several clouds are presented.