Priced from £30,795 in entry-level SE Technology trim, the Octavia iV is said to be the "most fuel-efficient Octavia ever built", achieving between 188.3mpg and 282.5mpg on the WLTP combined cycle while emitting 22-33g/km of CO2.
The PHEV takes its power from a 1.4-litre turbocharged petrol four-cylinder engine and an 127bhp electric motor for total outputs of 201bhp and 258lb ft.
The same system features in the larger Superb iV and, in a higher state of tune, the hot Octavia vRS iV, which will also become available to order next week.
A 13kWh battery pack gives the Octavia iV an official electric-only range of 43 miles and can be charged at rates of up to 3.6kW in as little as three-and-a-half hours.
The Octavia iV is supplied with both a 16A Type 2 charging cable and a 10A three-pin cable.
A range of driving modes are available, including E-mode, Hybrid, Hybrid Auto and Sport, which each offer different combinations of electric and combustion power.
Like any Octavia, the iV is available as both an estate and a hatchback, with prices climbing to £33,605 for the range-topping SE L Estate. All iV options are eligible for a 6% business-in-kind tax rate, making the iV an especially attractive option for fleet buyers.
With this latest addition, the Octavia is now available with petrol, diesel, mild-hybrid and plug-in hybrid powertrains.