Diphenylgermylene (Ph₂Ge) and its Ge=Ge doubly-bonded dimer, tetraphenyldigermene (6a), have been characterized directly in solution for the first time, by laser flash photolysis of 3,4-dimethyl-1,1-diphenylgermacyclopent-3-ene (4a). Steady state (lamp) photolysis of 4a in the presence of methanol, acetic acid, isoprene, or triethylsilane affords the expected trapping products of Ph₂Ge in chemical yields of >95% and a quantum yield of 0.55, while high intensity laser photolysis of 4a in the presence of millimolar concentrations of methanol affords the product of 1,2-addition of the alcohol to digermene 6a in addition to the germylene-alcohol adduct. Flash photolysis of 4a in dry deoxygenated hexane at 23 ^oC leads to the prompt formation of a transient assigned to Ph₂Ge (l_max=500 nm; e_max=1850 M^-1cm^-1), which decays with second-order kinetics (t ~ 3 ms). A rate constant of k_dim = 1.2 x 10¹⁰ M^-1s^-1 for the dimerization of Ph₂Ge has been estimated from the data. The decay of the germylene is accompanied over the same timescale by the formation of a second species assigned to digermene 6a (t ~ 40 ms; l_max = 440 nm), which also decays with second-order kinetics. Analogous results are obtained from 1,1-dimesityl-3,4-dimethylgermacyclopent-3-ene (4b), which affords the known Mes₂Ge (t ~ 20 ms; l_max = 560 nm) and tetramesityldigermene (l_max = 410 nm); the results for this system are compared to the analogous ones from laser flash photolysis of hexamesitylcyclotrigermane, from which has been estimated an absolute rate constant of k_dim = 6 x 10⁹ M^-1s^-1 for the dimerization of Mes₂Ge in hexane solution at 23 ^oC. The rates of decay of the signals due to Ph₂Ge and Mes₂Ge are accelerated upon addition of germylene scavengers such as n-butyl amine and acetic acid and the formation of the secondary (digermene) product is quenched; absolute rate constants for reaction with these reagents are reported. 1,1,3,4-Tetramethylgermacyclopent-3-ene (4c) has also been studied by (193 nm) laser flash photolysis, and yields transients assigned to Me₂Ge (t ~ 2 ms; l_max = 480 nm) and tetramethyldigermene (6c; l_max = 375 nm) on the basis of comparisons to the known gas- or solution-phase spectra of these compounds. The spectra of the three germylenes and two of the digermenes are in excellent agreement with calculated spectra, derived from time-dependent DFT calculations.