SnSe has emerged as an efficient thermoelectric material since a high value of the thermoelectric figure of merit (ZT) has been reported recently. Here we show with systematic angle resolved photoemission spectroscopy data that the low-lying electronic structures of undoped and hole-doped SnSe crystals exhibit noticeable temperature variation from 80 to 600 K. In particular, the hole effective masses for the two lowest lying valence band maxima are found to be very large and increase with decreasing temperature. Thermoelectric parameters derived from such hole-mass enhancement agree well with the transport values, indicating comprehensively a reduced impact of multivalley transport to the system's thermoelectric performance.