Why is it "behead" and not "dehead"?

Solution 1:

We didn’t use de-head be­cause we al­ready had a verb be­head by the time we start­ed us­ing de- to cre­ate verbs: be­head was a verb in Old English, be­héaf­di­an.

So be­head was al­ready used long be­fore the de- pri­va­tive pre­fix came to be used pro­duc­tive­ly in English. That didn’t hap­pen un­til Modern English with a few pro­duc­tive ex­am­ples in the 17ᵗʰ cen­tu­ry but most com­ing from the 19ᵗʰ cen­tu­ry or af­ter. As Ja­nus men­tions in com­ments, the de- word mean­ing the same thing, de­cap­i­tate, was im­port­ed in full with the de- al­ready there, from Latin via French, in the 17ᵗʰ cen­tu­ry.

There are many dif­fer­ent pos­si­ble sens­es of be- in verbs; the OED lists six dif­fer­ent pri­ma­ry sens­es with sub­sens­es. This here in be­head is one of the rar­er ones. Un­der be- sense 6c, it says that this pri­va­tive sense of be- used to cre­ate be­head is an an­cient sense that means be­reave of:

  1. Form­ing trans. verbs on sub­stan­tives used in an in­stru­men­tal re­la­tion; the pri­ma­ry idea be­ing;

    • a. To sur­round, cov­er, or be­daub with, as in be­cloud, to put clouds about, cov­er with clouds, be­dew. Thence, by ex­ten­sion,
    • b. To af­fect with in any way, as in be­night, be­guile, be­friend. In both sets there is of­ten an ac­com­pa­ny­ing no­tion of ‘thor­ough­ly, ex­ces­sive­ly,’ as in 2.
    • c. An an­cient ap­pli­ca­tion, no longer in liv­ing use, was to ex­press the sense of ‘be­reave of,’ as in be­head, be­limb, etc., q.v. Cf. 3, above.

Al­though 6a and 6b are still pro­duc­tive, 6c no longer is so in the liv­ing lan­guage. Another Old English verb formed us­ing 6c was belandian, mean­ing to de­prive of one’s land. How­ev­er, this verb did not sur­vive in­to Modern English.

El destierro

Apro­pos de na­da, the Span­ish equiv­a­lent of the ob­so­lete verb be­land still very much ex­ists in the verb des­te­rrar, which com­bines the pri­va­tive des‑ pre­fix with the noun tie­rra mean­ing land then puts that in­to an in­fini­tive verb form. This is nor­mal­ly trans­lat­ed as “ex­ile” in English, but some­time as “ex­pel” or as a noun “ex­pul­sion”. There is al­so a sub­stan­tive ver­sion, destier­ro, is fa­mous­ly found in “Can­tar del des­tie­rro”, which is the ti­tle of the first can­to from that most an­cient of Cas­til­ian epic po­ems, El Can­tar de Mio Cid.

Tru­ly, el Cid was be­land­ed of his lands by the King.

Solution 2:

From wiktionary:be- (rare or no longer productive) Off, away, over, across

becut, bedeal, betake, bego, behead, belimb, beland, benim, bereave, besleeve, betrunk

Solution 3:

Behead.

From Saxon Be-=('to') and heawian=hew=cut off. The original is "Beheawon heafde" to cut off the head.

From "Beheawon heafde" to "Beheawonheafde" to "Beheafde" to "Behead". ( somewhere through the ages some lexicographer did away with the double 'hea' and further surgery carried out resulted to "Beheafde" and later "Behead".)

Be- [Germanic 'be'] is often used as a prefix. When prefixed to verbs, be- frequently expresses an active signification, as behabban to surround; begangan to perform or dispatch, &c. Sometimes be- prefixed indicates no perceptible variation in the sense ; as belifan to be remaining, or over and above, begyrdan to begird or gird, as in sprengan and bespren- gan to sprinkle, or besprinkle.

(1726 English Etymology Dictionary) (Anglo-Saxon Dictionary 1888)